CN102866585B - Novel compound and method of producing the same, acid generator, resist composition and method of forming resist - Google Patents

Novel compound and method of producing the same, acid generator, resist composition and method of forming resist Download PDF

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CN102866585B
CN102866585B CN201210243584.6A CN201210243584A CN102866585B CN 102866585 B CN102866585 B CN 102866585B CN 201210243584 A CN201210243584 A CN 201210243584A CN 102866585 B CN102866585 B CN 102866585B
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compound
alkyl
group
acid
carbon number
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CN102866585A (en
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羽田英夫
内海义之
石塚启太
松泽贤介
金子文武
大下京子
清水宏明
吉井靖博
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Tokyo Ohka Kogyo Co Ltd
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Priority claimed from JP2008056880A external-priority patent/JP5186249B2/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/0285—Silver salts, e.g. a latent silver salt image
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/06—Silver salts
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G03F7/322—Aqueous alkaline compositions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H01L21/0274—Photolithographic processes

Abstract

The invention relates to a resist composition including a base component (A) which exhibits changed solubility in an alkali developing solution under action of acid and an acid-generator component (B) which generates acid upon exposure, the acid-generator component (B) including an acid generator (B1) consisting of a compound represented by general formula (b1-1) shown below: wherein Rx represents a hydrocarbon group which may have a substituent exclusive of a nitrogen atom; each of Q2 and Q3 independently represents a single bond or a divalent linkage group; Y1 represents an alkylene group of 1 to 4 carbon atoms or a fluorinated alkyl group; and Z+ represents an organic cation exclusive of an ion represented by general formula general formula (w-1).

Description

New compound and manufacture method thereof, acid agent, anti-corrosion agent composition and resist pattern formation method
The application is 200810185226.8 divisional application, and the applying date of original application is on Dec 18th, 2008, and the denomination of invention of original application is new compound and manufacture method, acid agent, anti-corrosion agent composition and resist pattern formation method
Technical field
The present invention relates to be used as new compound and manufacture method, acid agent, anti-corrosion agent composition and the resist pattern formation method of anti-corrosion agent composition acid agent and can conduct be used as new compound and the manufacture method thereof that anti-corrosion agent composition uses the intermediate of the compound of acid agent to use.
The application requires the right of priority of No. 2007-331163, the Patent that Patent No. 2007-330891,2007 12 years 21 days that on Dec 21st, 2007 proposes in Japan proposes in Japan and the Patent proposing in Japan on March 6th, 2008 No. 2008-056880, quotes its content at this.
Background technology
In photoetching technique, carry out following operation: for example on substrate, form the resist film being formed by anticorrosive additive material, use up, electron ray isoradial carries out selectivity exposure to this resist film, implement development treatment, thereby on above-mentioned resist film, form the resist pattern of regulation shape.The anticorrosive additive material that part after exposure is changed to the characteristic of dissolving in developer solution is called eurymeric, and the anticorrosive additive material that the part after exposure is changed to the characteristic that is insoluble to developer solution is called minus.
In recent years, in the manufacture of semiconductor element and liquid crystal display cells, along with the progress of photoetching technique, the miniaturization development of pattern rapidly.
As the method for miniaturization, normally make the wavelength of exposure light source shorten.Particularly, adopted the ultraviolet ray taking g line, i line as representative in the past, but start now to adopt KrF excimer laser or ArF excimer laser to carry out the batch production of semiconductor element.In addition, studying the short F of the above-mentioned excimer laser of wavelength ratio 2excimer laser, electron ray, EUV (extreme ultraviolet) and X ray etc.
Be accompanied by the short wavelengthization of exposure light source, seek anticorrosive additive material and improve with respect to the sensitivity of exposure light source, the photolithographic characteristics such as exploring degree that can reproduce the pattern of fine sizes.As the anticorrosive additive material that meets this requirement, known have contain the dissolubility to alkaline developer changes under sour effect base material component and by the chemically amplified photoresist of the acidic acid agent composition that exposes to.
In the past; as the base material component of this chemically amplified photoresist; the main resin that adopts, for example, use the part of polycarboxylated styrene (PHS) or its hydroxyl to be acid hydrolysis to be acid hydrolysis from the resin of property dissolution inhibition base protection from the PHS resinoids such as the resin of property dissolution inhibition base protection, a part derivative by (methyl) acrylate and the multipolymer that comes or its carboxyl etc.
In addition, " (methyl) acrylate " refers to a side or two sides in the acrylate of α position and hydrogen atom bonding and the methacrylate of α position and methyl bonding." (methyl) acrylates " refers to a side or two sides in the acrylates of α position and hydrogen atom bonding and the methacrylate of α position and methyl bonding." (methyl) acrylic acid " refers to a side or two sides in the acrylic acid of α position and hydrogen atom bonding and the methacrylic acid of α position and methyl bonding.
Up to now, proposed the multiple acid agent using in chemically amplified photoresist, known have (for example, with reference to patent documentations 1) such as the such as salt such as salt compounded of iodine, sulfonium salt acid agents.
Patent documentation 1: Japanese Patent Laid-Open 2003-241385 communique
As above-mentioned salt acid agent, general employing has the salt acid agent of perfluoro alkyl sulfonic acid ion as negative ion portion (acid) now.
But this salt acid agent compatibility to alkaline developer its structure is low, and be difficult to homogeneous distribution in resist film, likely the photolithographic characteristics such as exploring degree caused to harmful effect.
In addition, the perfluoroalkyl chain of above-mentioned negative ion portion, due to the sour diffusion that can suppress after exposure, therefore thinks that the longer the better, but the perfluoroalkyl chain that carbon number is 6～10 is difficult to decompose.For this reason, from considering the handling safety aspect of the biosome property accumulated, use carbon number be perfluoro alkyl sulfonic acid ion below 4, such as the ninth of the ten Heavenly Stems fluorine butane azochlorosulfonate acid ion etc.
Therefore, demand has the salt compounds that is compared to the more useful negative ion portion of anti-corrosion agent composition acid agent, intermediate that meanwhile also need to be useful in the time manufacturing this compound.
Summary of the invention
The present invention is the invention In view of the foregoing completing, and its object is to provide the new compound and the manufacture method thereof that use as the new compound of anti-corrosion agent composition acid agent and manufacture method, acid agent, anti-corrosion agent composition and resist pattern formation method and the intermediate can be as the synthetic compound as anti-corrosion agent composition acid agent time.
To achieve these goals, the present invention adopts following formation.
; the 1st mode of the present invention is a kind of anti-corrosion agent composition; it is to contain the base material component that the dissolubility to alkaline developer changes under sour effect (A) and by exposing to the anti-corrosion agent composition of acidic acid agent composition (B); it is characterized in that; above-mentioned acid agent composition (B) contains the acid agent (B1) being formed by the compound of following general formula (b1-1) expression
In formula, R xbe to there is substituent alkyl, but substituting group is not nitrogen-atoms; Q 2and Q 3be the linking group of singly-bound or divalent independently respectively; Y 1that carbon number is 1～4 alkylidene or fluoro alkylidene; Z +be organic cation, but be not the ion that following general formula (w-1) represents,
In formula, R 3～R 6maybe can there is substituent alkyl for hydrogen atom independently respectively, R 3～R 6in at least 1 be above-mentioned alkyl, R 3～R 6in at least 2 can be bonded to respectively ring.
The 2nd mode of the present invention is a kind of resist pattern formation method, and it comprises: use the anti-corrosion agent composition of above-mentioned the 1st mode on supporter, to form the operation of resist film; By the operation of above-mentioned resist film exposure; And above-mentioned resist film is carried out to the operation that alkali develops to form resist pattern.
The 3rd mode of the present invention is the compound (hereinafter referred to as compound (b1-1)) that following general formula (b1-1) represents.
[in formula, R xbe to there is substituent alkyl, but substituting group is not nitrogen-atoms; Q 2and Q 3be the linking group of singly-bound or divalent independently respectively; Y 1that carbon number is 1～4 alkylidene or fluoro alkylidene; Z +be organic cation, but be not the ion that following general formula (w-1) represents.]
[in formula, R 3～R 6maybe can there is substituent alkyl for hydrogen atom independently respectively, R 3～R 6in at least 1 be above-mentioned alkyl, R 3～R 6in at least 2 can be bonded to respectively ring.]
The 4th mode of the present invention is a kind of manufacture method of compound, and it comprises: the operation (hereinafter referred to as the manufacture method of compound (b1-1)) of reacting the compound (b1-1) that obtains following general formula (b1-1) expression by the compound (b0-02) that the compound (b0-1) of following general formula (b0-1) expression is represented with following general formula (b0-02).
Z +A -...(b0-02)
[in formula, R xbe to there is substituent alkyl, but substituting group is not nitrogen-atoms; Q 2and Q 3be the linking group of singly-bound or divalent independently respectively; Y 1that carbon number is 1～4 alkylidene or fluoro alkylidene; W +it is the ion that alkali metal ion or following general formula (w-1) represent; Z +be organic cation, but be not the ion that following general formula (w-1) represents; A -it is non-nucleophilicity negative ion.]
[in formula, R 3～R 6maybe can there is substituent alkyl for hydrogen atom independently respectively, R 3～R 6in at least 1 be above-mentioned alkyl, R 3～R 6in at least 2 can be bonded to respectively ring.]
The 5th mode of the present invention is a kind of acid agent, and its compound by above-mentioned the 3rd mode forms.
The 6th mode of the present invention is a kind of compound, and it represents (hereinafter referred to as compound (b0-1)) by following general formula (b0-1).
[in formula, R xbe to there is substituent alkyl, but substituting group is not nitrogen-atoms; Q 2and Q 3be the linking group of singly-bound or divalent independently respectively; Y 1that carbon number is 1～4 alkylidene or fluoro alkylidene; R 3～R 6maybe can there is substituent alkyl for hydrogen atom independently respectively, R 3～R 6in at least 1 be above-mentioned alkyl, R 3～R 6in at least 2 can be bonded to respectively ring.]
The 7th mode of the present invention is a kind of manufacture method of compound, and it comprises: react the operation (hereinafter referred to as the manufacture method (1) of compound (b0-1)) of the compound (b0-1) that obtains following general formula (b0-1) expression with amine or ammonium salt by the compound (1-11) that following general formula (1-11) is represented, the compound (1-12) of following general formula (1-12) expression.
R X-Q 3-X 21...(1-12)
[in formula, R xbe to there is substituent alkyl, but substituting group is not nitrogen-atoms; Q 2and Q 3be the linking group of singly-bound or divalent independently respectively; Y 1that carbon number is 1～4 alkylidene or fluoro alkylidene; R 3～R 6maybe can there is substituent alkyl for hydrogen atom independently respectively, R 3～R 6in at least 1 be above-mentioned alkyl, R 3～R 6in at least 2 can be bonded to respectively ring; X 21for halogen atom; M +for alkali metal ion.]
The 8th mode of the present invention is a kind of manufacture method of compound, and it comprises: react the operation (hereinafter referred to as the manufacture method (2) of compound (b0-1)) of the compound (b0-1) that obtains following general formula (b0-1) expression with amine or ammonium salt by the compound (1-21) that following general formula (1-21) is represented, the compound (1-12) of following general formula (1-12) expression.
R X-Q 3-X 21...(1-12)
[in formula, R xbe to there is substituent alkyl, but substituting group is not nitrogen-atoms; Q 2and Q 3be the linking group of singly-bound or divalent independently respectively; Y 1that carbon number is 1～4 alkylidene or fluoro alkylidene; R 3～R 6maybe can there is substituent alkyl for hydrogen atom independently respectively, R 3～R 6in at least 1 be above-mentioned alkyl, R 3～R 6in at least 2 can be bonded to respectively ring; R 3'～R 6' maybe can there is substituent alkyl for hydrogen atom independently respectively, R 3'～R 6' at least 1 be above-mentioned alkyl, R 3'～R 6' at least 2 can be bonded to respectively ring; X 21for halogen atom.]
The 9th mode of the present invention is a kind of compound, and it is the compound (1-21) being represented by following general formula (1-21).
[in formula, Q 2it is the linking group of singly-bound or divalent; Y 1that carbon number is 1～4 alkylidene or fluoro alkylidene; R 3'～R 6' maybe can there is substituent alkyl for hydrogen atom independently respectively, R 3'～R 6' at least 1 be above-mentioned alkyl, R 3'～R 6' at least 2 can be bonded to respectively ring.]
The 10th mode of the present invention is a kind of manufacture method of compound, and it comprises: the operation (hereinafter referred to as the manufacture method of compound (1-21)) of reacting the compound (1-21) that obtains following general formula (1-21) expression by the compound (1-11) that following general formula (1-11) is represented with ammonium salt.
[in formula, Q 2it is the linking group of singly-bound or divalent; Y 1that carbon number is 1～4 alkylidene or fluoro alkylidene; R 3'～R 6' maybe can there is substituent alkyl for hydrogen atom independently respectively, R 3'～R 6' at least 1 be above-mentioned alkyl, R 3'～R 6' at least 2 can be bonded to respectively ring; M +for alkali metal ion.]
The 11st mode of the present invention is a kind of manufacture method of compound, and it comprises: the operation (hereinafter referred to as the manufacture method of compound (1-14)) of reacting the compound (1-14) that obtains following general formula (1-14) expression by the compound (1-13) that following general formula (1-13) is represented with ammonium salt.
[in formula, R cbe to there is substituent alkyl, but substituting group is not nitrogen-atoms; Q 4it is the linking group of singly-bound or divalent; N is 0 or 1; Y 1that carbon number is 1～4 alkylidene or fluoro alkylidene; R 3'～R 6' maybe can there is substituent alkyl for hydrogen atom independently respectively, R 3'～R 6' at least 1 be above-mentioned alkyl, R 3'～R 6' at least 2 can be bonded to respectively ring; M +for alkali metal ion.]
In the present specification and claims, " aliphatics " is the concept relative with aromatic series, is defined as group, the compound etc. without aromaticity.
" alkylidene ", in the situation that there is no specified otherwise, comprises the divalent saturated hydrocarbyl of straight chain shape, a chain and ring-type.
" alkyl ", in the situation that there is no specified otherwise, comprises 1 valency saturated hydrocarbyl of straight chain shape, a chain and ring-type." low alkyl group " is that carbon number is 1～5 alkyl.
" structural unit " refers to the monomeric unit (monomeric unit) that forms resinous principle (polymkeric substance).
The concept of " exposure " comprises all radiation exposures.
According to the present invention, can provide the new compound and the manufacture method thereof that use as the new compound of anti-corrosion agent composition acid agent and manufacture method, acid agent, anti-corrosion agent composition and resist pattern formation method and the intermediate can be as the synthetic compound as anti-corrosion agent composition acid agent time.
Embodiment
" compound (b0-1) "
First, the compound to the 6th mode of the present invention (b0-1) describes.
The compound (b0-1) of the 6th mode of the present invention is the compound representing with above-mentioned general formula (b0-1).
In formula (b0-1), R xalkyl can be aromatic hydrocarbyl, can be also aliphatic alkyl.
R xaromatic hydrocarbyl be the alkyl with aromatic ring, the carbon number of this aromatic hydrocarbyl is preferably 3～30, more preferably 5～30, more preferably 5～20, be particularly preferably 6～15, most preferably be 6～12.But this carbon number does not comprise the carbon number in substituting group.
As aromatic hydrocarbyl, specifically can enumerate that phenyl, biphenyl (biphenyl) base, fluorenes (fluorenyl) base, naphthyl, anthracene (anthryl) base, phenanthryl etc. are removed 1 hydrogen atom by aromatic hydrocarbon ring and aryl alkyl such as the aryl that obtains, benzyl, phenethyl, 1-naphthyl methyl, 2-naphthyl methyl, 1-naphthyl ethyl, 2-naphthyl ethyl etc.The carbon number of the alkyl chain in above-mentioned aryl alkyl is preferably 1～4, and more preferably 1～2, be particularly preferably 1.
This aromatic hydrocarbyl can have substituting group.A part that for example forms the carbon atom of the aromatic ring that this aromatic hydrocarbyl has can be replaced by heteroatoms, and the hydrogen atom that is bonded to the aromatic ring that this aromatic hydrocarbyl has also can be substituted base and replace.
As the former example, can enumerate the ring that forms above-mentioned aryl carbon atom a part by the heteroatoms such as oxygen atom, sulphur atom (but except nitrogen-atoms) replace the heteroaryl that obtains, a part for the carbon atom that forms the aromatic hydrocarbon ring in above-mentioned aryl alkyl is replaced the heteroaryl alkyl that obtains by above-mentioned heteroatoms etc.
As the substituting group of the aromatic hydrocarbyl in the latter's example, can enumerate such as alkyl, alkoxy, halogen atom, haloalkyl, hydroxyl, oxygen atom (=O) etc.
About the substituent alkyl as above-mentioned aromatic hydrocarbyl, the alkyl that preferably carbon number is 1～5, most preferable, ethyl, propyl group, normal-butyl, the tert-butyl group.
About the substituent alkoxy as above-mentioned aromatic hydrocarbyl, the alkoxy that preferably carbon number is 1～5, further preferred methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, tert-butoxy, most preferably methoxyl, ethoxy.
About the substituent halogen atom as above-mentioned aromatic hydrocarbyl, can enumerate fluorine atom, chlorine atom, bromine atoms, iodine atom etc., preferably fluorine atom.
About the substituent haloalkyl as above-mentioned aromatic hydrocarbyl, part or all of hydrogen atom that can enumerate abovementioned alkyl replaced by above-mentioned halogen atom and the group that obtains.
R xaliphatic alkyl can be representative examples of saturated aliphatic alkyl, can be also unsaturated fatty hydrocarbons base.Aliphatic alkyl can be any in straight chain shape, a chain, ring-type.
About R xaliphatic alkyl, can be to form the substituting group that the part of carbon atom of this aliphatic alkyl contained heteroatoms (but except nitrogen-atoms) to replace, can be also that part or all substituting group that is contained heteroatoms (but except nitrogen-atoms) that forms the hydrogen atom of this aliphatic alkyl replaces.
As R xin " heteroatoms ", as long as the atom beyond carbon atom, hydrogen atom and nitrogen-atoms, be not particularly limited, can enumerate such as halogen atom, oxygen atom, sulphur atom etc.
As halogen atom, can enumerate fluorine atom, chlorine atom, iodine atom, bromine atoms etc.
The substituting group that contains heteroatoms (but except nitrogen-atoms) can be the substituting group only being formed by above-mentioned heteroatoms, can be also to contain group beyond above-mentioned heteroatoms or the group of atom.
As replacing the substituting group of a part of carbon atom, specifically for example can enumerate-O-,-C (=O)-O-,-C (=O)-,-O-C (=O)-O-,-S-,-S (=O) 2-,-S (=O) 2-O-etc.In the time that aliphatic alkyl is ring-type, also can in ring structure, contain these substituting groups.
As the substituting group that replaces part or all hydrogen atom, specifically can enumerate such as alkoxy, halogen atom, haloalkyl, hydroxyl, oxygen atom (=O) etc.
As above-mentioned alkoxy, the alkoxy that preferably carbon number is 1～5, further preferred methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, tert-butoxy, most preferably methoxyl, ethoxy.
As above-mentioned halogen atom, can enumerate fluorine atom, chlorine atom, bromine atoms, iodine atom etc., preferably fluorine atom.
As above-mentioned haloalkyl, can enumerate carbon number and be 1～5 alkyl, part or all of the hydrogen atom of the alkyl such as such as methyl, ethyl, propyl group, normal-butyl, the tert-butyl group replaced by above-mentioned halogen atom and the group that obtains.
As aliphatic alkyl, the preferably saturated hydrocarbyl of straight chain shape or a chain, straight chain shape or 1 valency unsaturated alkyl of chain or the aliphatic alkyl (alicyclic group) of ring-type.
As the saturated hydrocarbyl (alkyl) of straight chain shape, preferably carbon number is 1～20, more preferably 1～15, most preferably be 1～10.Particularly, can enumerate such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, myristyl, pentadecyl, cetyl, isocetyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl etc.
As the saturated hydrocarbyl (alkyl) of chain, preferably carbon number is 3～20, more preferably 3～15, most preferably be 3～10.Particularly, can enumerate such as 1-Methylethyl, 1-methyl-propyl, 2-methyl-propyl, 1-methyl butyl, 2-methyl butyl, 3-methyl butyl, 1-ethyl-butyl, 2-ethyl-butyl, 1-methyl amyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl etc.
As unsaturated alkyl, preferably carbon number is 2～10, more preferably 2～5, more preferably 2～4, be particularly preferably 3.As 1 valency unsaturated alkyl of straight chain shape, can enumerate such as vinyl, propenyl (allyl), butenyl group etc.As 1 valency unsaturated alkyl of a chain, can enumerate such as 1-methylpropenyl, 2-methylpropenyl etc.
Propenyl particularly preferably in above-mentioned unsaturated alkyl.
As alicyclic group, can be monocycle base, can be also many cyclic groups.Its carbon number is preferably 3～30, and more preferably 5～30, more preferably 5～20, be particularly preferably 6～15, most preferably be 6～12.
Particularly, can enumerate the group of for example removing 1 above hydrogen atom by mononaphthene and obtain; Removed group that more than 1 hydrogen atom obtains etc. by polynaphthenes such as dicyclo alkane, three cycloalkanes, tetracycloalkanes.More specifically, can enumerate the group of for example removing 1 above hydrogen atom by the mononaphthene such as cyclopentane, cyclohexane and obtain; Remove more than 1 hydrogen atom and group of obtaining etc. by polynaphthenes such as diamantane, norbornane, isoborneol alkane, tristane, Fourth Ring dodecanes.
In the time that alicyclic group does not have containing heteroatomic substituting group in its ring structure, as alicyclic group, preferred many cyclic groups, further preferably remove more than 1 hydrogen atom by polynaphthene and the group that obtains, most preferably remove more than 1 hydrogen atom by diamantane and the group that obtains.
In the time that alicyclic group has containing heteroatomic substituting group in its ring structure, contain heteroatomic substituting group as this, preferably-O-,-C (=O)-O-,-S-,-S (=O) 2-,-S (=O) 2-O-.As the object lesson of described alicyclic group, can enumerate such as following formula (L1)～(L5), (S1)～(S4) etc.
[in formula, Q " be that carbon number is 1～5 alkylidene ,-O-,-S-,-O-R 94-or-S-R 95-, R 94and R 95be respectively that carbon number is 1～5 alkylidene independently, m is 0 or 1 integer.]
As Q " alkylidene, can enumerate and above-mentioned R 1the identical group of alkylidene.
As R 94and R 95alkylidene, can enumerate and above-mentioned R 1the identical group of alkylidene.
About these alicyclic groups, a part that is bonded to the hydrogen atom on the carbon atom that forms its ring structure can be substituted base and replace.As this substituting group, can enumerate such as alkyl, alkoxy, halogen atom, haloalkyl, hydroxyl, oxygen atom (=O) etc.
As abovementioned alkyl, the alkyl that preferably carbon number is 1～5, particularly preferably methyl, ethyl, propyl group, normal-butyl, the tert-butyl group.
About above-mentioned alkoxy, halogen atom, can enumerate respectively with as replace above-mentioned hydrogen atom part or all substituting group and the identical group of the group enumerated.
In the present invention, as R x, preferably can there is substituent straight chain-like alkyl, maybe can there is substituent cyclic group.As this cyclic group, can be to there is substituent aromatic hydrocarbyl, can be also to there is substituent alicyclic group, further preferably can there is substituent alicyclic group.
As above-mentioned aromatic hydrocarbyl, preferably can there is substituent naphthyl and maybe can there is substituent phenyl.
As thering is substituent alicyclic group, preferably can there is substituent polycycle alicyclic group.As this polycycle alicyclic group, preferably remove more than 1 hydrogen atom by above-mentioned polynaphthene and the group obtaining, above-mentioned (L2)～(L5), (S3)～(S4) etc., wherein preferred adamantyl.
Q 2and Q 3be the linking group of singly-bound or divalent independently respectively.
As the linking group of divalent, such as can enumerate alkylidene, containing heteroatomic group (hereinafter referred to as containing heteroatomic linking group) etc.
Refer to the atom beyond carbon atom and hydrogen atom containing " heteroatoms " in heteroatomic linking group, can enumerate such as oxygen atom, sulphur atom, nitrogen-atoms etc.
About the alkylidene as divalent linking group, can be straight chain shape, can be also a chain.The carbon number of this alkylidene is preferably 1～12, and more preferably 1～5, be particularly preferably 1～3.
As this alkylidene, specifically can enumerate for example methylene [CH 2-];-CH (CH 3)-,-CH (CH 2cH 3)-,-C (CH 3) 2-,-C (CH 3) (CH 2cH 3)-,-C (CH 3) (CH 2cH 2cH 3)-,-C (CH 2cH 3) 2-wait alkyl methylene; Ethylidene [CH 2cH 2-];-CH (CH 3) CH 2-,-CH (CH 3) CH (CH 3)-,-C (CH 3) 2cH 2-,-CH (CH 2cH 3) CH 2-wait alkyl ethylidene; Trimethylene (positive propylidene) [CH 2cH 2cH 2-];-CH (CH 3) CH 2cH 2-,-CH 2cH (CH 3) CH 2-wait alkyl trimethylene; Tetramethylene [CH 2cH 2cH 2cH 2-];-CH (CH 3) CH 2cH 2cH 2-,-CH 2cH (CH 3) CH 2cH 2-wait alkyl tetramethylene; Pentamethylene [CH 2cH 2cH 2cH 2cH 2-] etc.
As containing heteroatomic linking group, can enumerate for example oxygen atom (ehter bond;-O-), sulphur atom (thioether bond;-S-), the non-hydrocarbons such as-NH-key (H can be replaced by the substituting group such as alkyl, acyl group), ester bond (C (=O)-O-), amido link (C (=O)-NH-), carbonyl (C (=O)-), carbonic acid ester bond (O-C (=O)-O-) is containing heteroatomic linking group; This non-hydrocarbons is containing the composition of heteroatomic linking group and above-mentioned alkylidene.As said composition, for example can enumerate-R 91-O-,-R 92-O-C (=O)-,-C (=O)-O-R 93-(R in formula 91～R 93be respectively alkylidene independently) etc. or their composition.As R in above formula 91～R 93alkylidene, can enumerate the group identical with the alkylidene of enumerating as above-mentioned divalent linking group.
As Q 2, preferably carbonyl, singly-bound ,-R 92-O-C (=O)-.
As Q 3, preferably singly-bound, alkylidene, carbonyl.
Particularly preferably Q 2for carbonyl and Q 3for singly-bound or Q 2for singly-bound and Q 3for alkylidene or Q 2for-R 92-O-C (=O)-and Q 3for carbonyl.
In formula (b0-1), Y 1that carbon number is 1～4 alkylidene or fluoro alkylidene.
As Y 1alkylidene, the identical group of alkylidene that can to enumerate with carbon number in the alkylidene of enumerating as above-mentioned divalent linking group be 1～4.As fluoro alkylidene, part or all of hydrogen atom that can enumerate this alkylidene replaced the group obtaining by fluorine atom.
As Y 1, specifically can enumerate-CF 2-,-CF 2cF 2-,-CF 2cF 2cF 2-,-CF (CF 3) CF 2-,-CF (CF 2cF 3)-,-C (CF 3) 2-,-CF 2cF 2cF 2cF 2-,-CF (CF 3) CF 2cF 2-,-CF 2cF (CF 3) CF 2-,-CF (CF 3) CF (CF 3)-,-C (CF 3) 2cF 2-,-CF (CF 2cF 3) CF 2-,-CF (CF 2cF 2cF 3)-,-C (CF 3) (CF 2cF 3)-;-CHF-,-CH 2cF 2-,-CH 2cH 2cF 2-,-CH 2cF 2cF 2-,-CH (CF 3) CH 2-,-CH (CF 2cF 3)-,-C (CH 3) (CF 3)-,-CH 2cH 2cH 2cF 2-,-CH 2cH 2cF 2cF 2-,-CH (CF 3) CH 2cH 2-,-CH 2cH (CF 3) CH 2-,-CH (CF 3) CH (CF 3)-,-C (CF 3) 2cH 2-;-CH 2-,-CH 2cH 2-,-CH 2cH 2cH 2-,-CH (CH 3) CH 2-,-CH (CH 2cH 3)-,-C (CH 3) 2-,-CH 2cH 2cH 2cH 2-,-CH (CH 3) CH 2cH 2-,-CH 2cH (CH 3) CH 2-,-CH (CH 3) CH (CH 3)-,-C (CH 3) 2cH 2-,-CH (CH 2cH 3) CH 2-,-CH (CH 2cH 2cH 3)-,-C (CH 3) (CH 2cH 3)-etc.
As Y 1, preferably fluoro alkylidene, is particularly preferably bonded to the fluoro alkylidene that the carbon atom of adjacent sulphur atom is replaced by fluorine.As such fluoro alkylidene, can enumerate-CF 2-,-CF 2cF 2-,-CF 2cF 2cF 2-,-CF (CF 3) CF 2-,-CF 2cF 2cF 2cF 2-,-CF (CF 3) CF 2cF 2-,-CF 2cF (CF 3) CF 2-,-CF (CF 3) CF (CF 3)-,-C (CF 3) 2cF 2-,-CF (CF 2cF 3) CF 2-;-CH 2cF 2-,-CH 2cH 2cF 2-,-CH 2cF 2cF 2-;-CH 2cH 2cH 2cF 2-,-CH 2cH 2cF 2cF 2-,-CH 2cF 2cF 2cF 2-etc.
Wherein, preferably-CF 2-,-CF 2cF 2-,-CF 2cF 2cF 2-or CH 2cF 2cF 2-, further preferably-CF 2-,-CF 2cF 2-or-CF 2cF 2cF 2-, particularly preferably-CF 2-.
In formula (b0-1), R 3～R 6maybe can there is substituent alkyl for hydrogen atom independently respectively, R 3～R 6in at least 1 be above-mentioned alkyl.
As R 3～R 6alkyl, can enumerate and above-mentioned R xidentical group.
This alkyl can be aliphatic alkyl, can be also aromatic hydrocarbyl.In the time that this alkyl is aliphatic alkyl, as this aliphatic alkyl, particularly preferably can there is substituent carbon number and be 1～12 alkyl.
The substituting group that can have as this alkyl, can enumerate with as above-mentioned R xthe alkyl substituting group that can have and the identical group of group enumerated, particularly preferably hydroxyl.In addition, can also there is substituting group for example nitrogen-atoms, cyano group (CN), the amino (NH of nitrogen atom 2), amide group (NH-C (=O)-) etc.
R 3～R 6in at least 1 be described alkyl, preferably 2 or 3 is described alkyl.
R 3～R 6in at least 2 can be bonded to respectively ring.For example, can be R 3～R 6in 2 bondings form 1 ring, can be also R 3～R 6in 3 bondings form 1 ring, can also be R 3～R 6in each 2 respectively bondings form 2 rings.
As R 3～R 6in at least 2 respectively bonding and with the ring (nitrogen atom is as heteroatomic heterocycle) forming together with nitrogen-atoms in formula, can be aliphatics heterocycle, can be also heteroaromatic.In addition, this heterocycle can be monocycle, can be also many rings.
As (the N of kation portion in formula (b0-1) +(R 3) (R 4) (R 5) (R 6)) object lesson, can enumerate by amine derive and come ammonium ion.
Here, " derived and the ammonium ion that comes by amine " and refer to the nitrogen-atoms of amine and the kation that hydrogen atom bonding forms, nitrogen-atoms and the quaternary ammonium ion that substituting group bonding forms of amine.
The amine of derivative above-mentioned ammonium ion can be fatty amine, can be also aromatic amine.
As fatty amine, particularly preferably ammonia NH 3at least 1 of hydrogen atom be that alkyl or hydroxyalkyl below 12 replaces the amine (alkyl amine or alkyl alcoholamine) or the cyclammonium that obtain by carbon number.
As the object lesson of alkyl amine and alkyl alcoholamine, can enumerate alkyl amines such as n-hexyl amine, n-heptyl amine, n-octylamine, n-nonyl amine, positive decyl amine; The dialkylamines such as diethylamide, di-n-propyl amine, two n-heptyl amine, di-n-octyl amine, dicyclohexyl amine; The trialkylamines such as Trimethylamine, triethylamine, three n-pro-pyl amine, tri-n-butyl amine, three n-hexyl amine, three n-pentyl amine, three n-heptyl amine, three n-octylamine, three n-nonyl amine, three positive decyl amine, three dodecyl amine; The alkyl alcoholamines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, two n-octyl alcohol amine, three n-octyl alcohol amine.
As cyclammonium, can enumerate and for example contain nitrogen-atoms as heteroatomic heterogeneous ring compound.As this heterogeneous ring compound, can be monocyclic compound (aliphatics monocycle amine), can be also polycyclic compund (aliphatics polycyclic amines).
As aliphatics monocycle amine, specifically can enumerate piperidines, piperazine etc.
As aliphatics polycyclic amines, the aliphatics polycyclic amines that preferably carbon number is 6～10, specifically can enumerate 1,5-diazo bicyclic [4.3.0]-5-nonene, 1,8-diazo bicyclic [5.4.0]-7-undecylene, hexamethylene tetramine, Isosorbide-5-Nitrae-diazo bicyclic [2.2.2] octane etc.
As aromatic amine, can enumerate aniline, pyridine, 4-dimethylaminopyridine (DMAP), pyrroles, indoles, pyrazoles, imidazoles etc.
As quaternary ammonium ion, can enumerate tetramethyl ammonium, tetraethyl ammonium ion, TBuA ion etc.
In the present invention, as (the N of kation portion in formula (b0-1) +(R 3) (R 4) (R 5) (R 6)), particularly preferably R 3～R 6in at least 1 kation portion that is alkyl and at least 1 and is hydrogen atom.
Wherein, preferred R 3～R 6in 3 be 1 kation (trialkyl ammonium ion) or R for hydrogen atom of alkyl and residue 3～R 6in 2 be 1 kation (dialkyl ammonium ion) for hydrogen atom of alkyl and residue.
Alkyl in trialkyl ammonium ion or dialkyl ammonium ion respectively independently preferably carbon number be 1～10, more preferably 1～8, most preferably be 1～5.Specifically can enumerate such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl etc.Wherein ethyl most preferably.
In the present invention, compound (b0-1) be preferably following general formula (b0-1-1) represent compound, be particularly preferably following general formula (b0-1-11) or (b0-1-12) represent compound.
[in formula, R x, Q 3, Y 1, R 3～R 6respectively with above-mentioned general formula (b0-1) in R x, Q 3, Y 1, R 3～R 6identical, n is 0 or 1.]
[in formula, n, Y 1, R 3～R 6respectively with above-mentioned general formula (b0-1-1) in n, Y 1, R 3～R 6identical, R 1alkylidene, R band R crespectively independently for thering is the alkyl of substituting group (but except nitrogen-atoms), Q 4singly-bound or alkylidene.]
In formula (b0-1-11), as R b, can enumerate and above-mentioned R xidentical group, preferably can have substituent straight chain shape or chain saturated hydrocarbyl, can there is substituent alicyclic group, maybe can there is substituent aromatic hydrocarbyl.Wherein, preferably the saturated hydrocarbyl of straight chain shape maybe can have substituent alicyclic group.
As R 1alkylidene, the preferably alkylidene of straight chain shape or a chain, the carbon number of this alkylidene is preferably 1～12, more preferably 1～5, be particularly preferably 1～3.As object lesson, can enumerate the group identical with the alkylidene of enumerating as above-mentioned divalent linking group.
As the R in formula (b0-1-12) c, can enumerate and above-mentioned R xidentical group, preferably can have substituent alicyclic group and maybe can have substituent aromatic hydrocarbyl.Wherein, preferably in its ring structure, have containing heteroatomic substituent alicyclic group.
As Q 4alkylidene, can enumerate the group identical with the alkylidene of enumerating as above-mentioned divalent linking group.
N is preferably 1.
As compound (b0-1), the compound of particularly preferably following general formula (b0-1-21)～(b0-1-22), (b0-1-31)～(b0-1-35) represent.
[in formula, d, e, f are respectively 1～10 integer independently, the integer that p is 1～3, and q1～q2 is respectively 1～5 integer independently, the integer that r1 is 0～3, the integer that g is 1～20, R 7for substituting group.]
[in formula, Q ", d, e, f, p be same as described above respectively, n1～n3 be independently respectively 0 or 1, v1～v5 be respectively 0～3 integer independently, w1～w5 is respectively 0～3 integer independently, R 7for substituting group.]
As R 7substituting group, can be set forth in above-mentioned R xthe substituting group that the middle substituting group that can have as aliphatic alkyl, aromatic hydrocarbyl can have and the identical group of group enumerated.
Work as R 7with symbol (r1, w1～w5) while being more than 2 integers, the multiple R in this compound 7respectively can be identical, also can be different.
Compound of the present invention (b0-1) is new compound.
Compound of the present invention (b0-1) can use as the intermediate in the time synthesizing the compound (the particularly compound of the 3rd mode of the present invention (b1-1)) that is used as anti-corrosion agent composition acid agent.
Compound of the present invention (b0-1) for example can adopt compound (b0-1) manufacture method (1) of the present invention described later the 7th mode or compound (b0-1) manufacture method (2) of the present invention's the 8th mode to manufacture.
" manufacture method (1) of compound (b0-1) "
Then, the compound to the present invention's the 7th mode (b0-1) manufacture method (1) describes.
The manufacture method (1) of compound of the present invention (b0-1) comprising: react to obtain by the compound (1-11) that following general formula (1-11) is represented, the compound (1-12) that following general formula (1-12) represents the compound (b0-1) that following general formula (b0-1) represents with amine or ammonium salt.
R X-Q 3-X 21...(1-12)
[in formula, R x, Q 2, Q 3, Y 1, R 3～R 6respectively with above-mentioned general formula (b0-1) in R x, Q 2, Q 3, Y 1, R 3～R 6identical; X 21for halogen atom; M +for alkali metal ion.]
As the M in formula (1-11) +, can enumerate sodion, potassium ion, lithium ion etc.
As compound (1-11), can use commercially available compound, also can synthesize.
For example,, when compound (1-11) is the Q in formula (1-11) 2while being the compound (hereinafter referred to as compound (1-11-1)) of carbonyl, can enumerating and comprise that the compound (0-1) by following general formula (0-1) is represented heat, neutralize the method that obtains the operation (hereinafter referred to as salt formation operation) of the compound (0-2) that following general formula (0-2) represents and above-claimed cpd (0-2) is heated to the operation (hereinafter referred to as carboxylic acidizing process) that obtains compound (1-11-1) in acid strength under higher than the sour existence of compound (1-11-1) under the existence of alkali.
[in formula, R 01for alkyl, Y 1, M +the same.]
As R 01alkyl, preferably the alkyl of straight chain shape or a chain, specifically can enumerate methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl, the tert-butyl group, amyl group, isopentyl, pungent amyl group etc.
Wherein, the alkyl that preferably carbon number is 1～4, most preferable.
As compound (0-1), can use commercially available product.
Form operation about salt, for example can be by compound (0-1) being dissolved, is added in solvent alkali in this solution, heating and implement.
As solvent, as long as the solvent of energy dissolved compound (0-1), can enumerate such as water, tetrahydrofuran etc.
As alkali, use the alkali corresponding with M in formula (0-2), as this alkali, can enumerate the alkali metal hydroxides such as NaOH, potassium hydroxide, lithium hydroxide.
About the consumption of alkali, with respect to 1 mole of compound (0-1), be preferably 1～5 mole, more preferably 2～4 moles.
Heating-up temperature is preferably 20～120 DEG C of left and right, more preferably 50～100 DEG C of left and right.Heat time is according to heating-up temperature etc. and different, and preferably 0.5～12 hour conventionally, further preferably 1～5 hour.
About the neutralization after above-mentioned heating, can implement by adding the acid such as hydrochloric acid, sulfuric acid, p-toluenesulfonic acid in the reactant liquor after above-mentioned heating.
Now, preferably make the pH (25 DEG C) of reactant liquor after acid is added 6～8 implement neutralization.In and time the temperature of reactant liquor be preferably 20～30 DEG C, more preferably 23～27 DEG C.
After reaction finishes, can separate the compound in reactant liquor (0-2), refine.Separate, refining can utilize existing known method, for example concentrated, solvent extraction, distillation, crystallization, recrystallization, chromatography etc., can use separately any in them, or two or more is used in combination.
In carboxylic acidizing process, by by form at above-mentioned salt the compound (0-2) that obtains in operation acid strength higher than the sour existence of compound (1-11-1) under heating obtain this compound (1-11-1).
" acid strength is higher than the acid (below sometimes referred to as strong acid) of compound (1-11-1) " refers to the acid of be less than in compound (1-11-1)-COOH of the value of pKa (25 DEG C).By using described strong acid, in compound (0-2)-COO-M +become-COOH, obtain compound (1-11-1).
As strong acid, can be from known acid the suitably acid of the pKa of be less than in above-claimed cpd (1-11-1)-COOH of choice for use pKa.In compound (1-11-1)-pKa of COOH can try to achieve by known titrimetry.
As strong acid, specifically can enumerate the sulfonic acid such as aryl sulfonic acid, alkyl sulfonic acid, sulfuric acid, hydrochloric acid etc.As aryl sulfonic acid, can enumerate for example p-toluenesulfonic acid.As alkyl sulfonic acid, can enumerate such as methane-sulforic acid, trifluoromethanesulfonic acid etc.As strong acid, from the viewpoint of the dissolubility to organic solvent and refining easiness, particularly preferably p-toluenesulfonic acid.
About carboxylic acidizing process, for example can be by compound (0-2) be dissolved in solvent, add after strong acid and heat and implement.
As solvent, as long as the solvent of energy dissolved compound (0-2), can enumerate such as acetonitrile, MEK etc.
About the consumption of strong acid, with respect to 1 mole of compound (0-2), be preferably 0.5～3 mole, more preferably 1～2 mole.
Heating-up temperature is preferably 20～150 DEG C of left and right, more preferably 50～120 DEG C of left and right.Heat time is according to heating-up temperature etc. and different, and preferably 0.5～12 hour conventionally, further preferably 1～5 hour.
After reaction finishes, can separate the compound in reactant liquor (1-11-1), refine.Separate, refining can utilize existing known method, for example concentrated, solvent extraction, distillation, crystallization, recrystallization, chromatography etc., can use separately any in them, or two or more is used in combination.
For example,, when compound (1-11) is the Q in formula (1-11) 2for-R 1-O-C (=O)-(in formula, R 1with above-mentioned R 92equally, for alkylidene) compound (hereinafter referred to as compound (1-11-2)) time, can enumerate the compound (0-3) comprising by following general formula (0-3) is represented and react the method for the operation that obtains compound (1-11-2) with above-claimed cpd (1-11-1).
HO-R 1-O-R 2...(0-3)
[in formula, R 1for alkylidene; R 2for thering is aromatic radical as substituent fat-based, Y 1for carbon number be 1～4 alkylidene or fluoro alkylidene; M +for alkali metal ion.]
Compound (0-3) is not particularly limited with the method that compound (1-11-1) reacts, for example can be by compound (0-3) being mixed, dissolve, heats and implement with compound (1-11-1) in solvent.
As solvent, can enumerate for example toluene, dichloro-benzenes, 1,2-ethylene dichloride, 1,3-propylene dichloride etc.
As heating-up temperature (temperature of reaction), preferably 20～140 DEG C of left and right, more preferably 60～130 DEG C of left and right.Heat time according to heating-up temperature etc. and different, is preferably 1～72 hour, more preferably 6～48 hours conventionally.
Above-mentioned reaction can be carried out under the existence of acidic catalyst.As acidic catalyst, be not particularly limited, can enumerate the such as sulfonic acid such as aryl sulfonic acid, alkyl sulfonic acid, sulfuric acid, hydrochloric acid etc.As aryl sulfonic acid, can enumerate for example p-toluenesulfonic acid.As alkyl sulfonic acid, can enumerate such as methane-sulforic acid, trifluoromethanesulfonic acid etc.Can use separately any in them, also can two or more share.As acidic catalyst, from the viewpoint of the dissolubility to organic solvent and refining easiness, particularly preferably p-toluenesulfonic acid.
About the consumption of acidic catalyst, with respect to 1 mole of compound (1-11-1), be preferably 0.1～2 mole, more preferably 0.1～1 mole.
After reaction finishes, can separate the compound in reactant liquor (1-11-2), refine.Separate, refining can utilize existing known method, for example concentrated, solvent extraction, distillation, crystallization, recrystallization, chromatography etc., can use separately any in them, or two or more is used in combination.
As the X in formula (1-12) 21halogen atom, can enumerate bromine atoms, chlorine atom, iodine atom, fluorine atom etc., from reactive excellent viewpoint, preferably bromine atoms or chlorine atom.
As compound (1-12), can use commercially available product.
As amine or ammonium salt, can use with formula (b0-1) in (the N of kation portion +(R 3) (R 4) (R 5) (R 6)) corresponding material.As the object lesson of this amine, can enumerate the amine of the derivative ammonium ion of above-mentioned conduct and the alkyl amine enumerated, dialkylamine, trialkylamine, aromatic amine etc.As the object lesson of ammonium salt, can enumerate the quaternary ammonium salts such as Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TBAH etc.
As the method that compound (1-11), compound (1-12) are reacted with amine or ammonium salt, be not particularly limited, can enumerate the method that for example makes compound (1-11), compound (1-12) contact with amine or ammonium salt in reaction dissolvent.In the solution that the method for example can obtain by dissolved compound in reaction dissolvent (1-11), adding compound (1-12) and amine or quaternary ammonium compound implements.
As reaction dissolvent, as long as energy dissolved compound (1-11) and compound (1-12), specifically can enumerate tetrahydrofuran (THF), acetone, dimethyl formamide (DMF), dimethyl acetamide, dimethyl sulfoxide (DMSO) (DMSO), acetonitrile etc.
About the addition of compound (1-12), with respect to compound (1-11), be preferably about 1～3 equivalent, further preferred 1～2 equivalent.
About the addition of amine or quaternary ammonium compound, with respect to compound (1-11), be preferably about 1～3 equivalent, further preferred 1～2 equivalent.
Temperature of reaction is preferably-20～40 DEG C, more preferably 0～30 DEG C.Reaction time according to reactivity and the temperature of reaction etc. of compound (1-11) and compound (1-12) and different, is preferably 1～120 hour, more preferably 1～48 hour conventionally.
After reaction finishes, can separate the compound in reactant liquor (b0-1), refine.Separate, refining can utilize existing known method, for example, wash, concentrate, solvent extraction, distillation, crystallization, recrystallization, chromatography etc., can use separately any in them, or two or more is used in combination.
In the present invention, compound (b0-1) has N +(R 3) (R 4) (R 5) (R 6) as kation portion, owing to being insoluble in water, therefore can refine by washing.
The structure of the compound (b0-1) obtaining can be passed through 1h-nuclear magnetic resonance (NMR) spectrometry, 13c-NMR spectrometry, 19the general Analytical Methods of Organic Compounds such as F-NMR spectrometry, infrared ray absorbing (IR) spectrometry, mass spectrum (MS) method, elemental microanalysis method, X ray crystal diffraction method are confirmed.
" manufacture method (2) of compound (b0-1), compound (1-21) "
Then, the compound (1-21) of the compound to the present invention's the 8th mode (b0-1) manufacture method (2) and the present invention ground 9 modes describes.
The manufacture method (2) of compound of the present invention (b0-1) comprises that the compound (1-21) by following general formula (1-21) is represented, the compound (1-12) of following general formula (1-12) expression react the operation of the compound (b0-1) that obtains following general formula (b0-1) expression with amine or ammonium salt.
R X-Q 3-X 21...(1-12)
[in formula, R x, Q 2, Q 3, Y 1, R 3～R 6respectively with above-mentioned general formula (b0-1) in R x, Q 2, Q 3, Y 1, R 3～R 6identical; R 3'～R 6' maybe can there is substituent alkyl for hydrogen atom independently respectively, R 3'～R 6' at least 1 be above-mentioned alkyl, R 3'～R 6' at least 2 respectively bonding form ring; X 21for halogen atom.]
As the R in formula (1-21) 3'～R 6', can enumerate respectively and above-mentioned R 3～R 6identical group.
In this manufacture method (2), (N of kation portion in formula (1-21) +(R 3') (R 4') (R 5') (R 6')) with formula (b0-1) in (the N of kation portion +(R 3) (R 4) (R 5) (R 6)) can be identical, also can be different, consider the simplification of operation etc., preferably identical.
About the operation that compound (1-21), compound (1-12) are reacted with amine or ammonium salt, except being replaced with compound (1-21), the compound (1-11) in above-mentioned manufacture method (1) can use the method identical with above-mentioned manufacture method (1) to implement.
The compound (1-21) using as parent material in this manufacture method (2) is novel compound.
Compound (1-21) for example can use the manufacture method of compound described later (1-21) to manufacture.
" manufacture method of compound (1-21) "
Then, the manufacture method of the compound to the present invention's the 10th mode (1-21) describes.
The manufacture method of compound of the present invention (1-21) comprises that the compound (1-11) by following general formula (1-11) is represented reacts the operation of the compound (1-21) that obtains following general formula (1-21) expression with ammonium salt.
In formula, Q 2, Y 1, R 3'～R 6', M +the same respectively.
As ammonium salt, can enumerate hydrochloride or the bromate etc. of abovementioned alkyl amine, dialkylamine, trialkylamine and aromatic amine.
About reacting of compound (1-11) and ammonium salt, can similarly implement with existing known salt method of replacing.For example, by water-soluble to compound (1-11) and ammonium salt, methylene chloride, acetonitrile, methyl alcohol, chloroform equal solvent, wait and make its reaction by stirring.
Temperature of reaction is preferably 0 DEG C～150 DEG C left and right, more preferably 0 DEG C～100 DEG C left and right.Reaction time according to reactivity and the temperature of reaction etc. of compound (1-11) and ammonium salt and different, is preferably 0.5～10 hour, more preferably 1～5 hour conventionally.
After reaction finishes, can separate the compound in reactant liquor (1-21), refine.Separate, refining can utilize existing known method, for example concentrated, solvent extraction, distillation, crystallization, recrystallization, chromatography etc., can use separately any in them, or two or more is used in combination.
The structure of the compound (1-21) obtaining can be passed through 1h-nuclear magnetic resonance (NMR) spectrometry, 13c-NMR spectrometry, 19the common Analytical Methods of Organic Compounds such as F-NMR spectrometry, infrared ray absorbing (IR) spectrometry, mass spectrum (MS) method, elemental microanalysis method, X ray crystal diffraction method are confirmed.
" manufacture method of compound (1-14) "
Then, the compound to the present invention's the 11st mode (1-14) manufacture method describes.
The manufacture method of compound of the present invention (1-14) comprises that the compound (1-13) by following general formula (1-13) is represented reacts the operation of the compound (1-14) that obtains following general formula (1-14) expression with ammonium salt.
[in formula, R cfor having substituent alkyl, but substituting group is not nitrogen-atoms; Q 4it is the linking group of singly-bound or divalent; N is 0 or 1; Y 1that carbon number is 1～4 alkylidene or fluoro alkylidene; R 3'～R 6' maybe can there is substituent alkyl for hydrogen atom independently respectively, R 3'～R 6' at least 1 be above-mentioned alkyl, R 3'～R 6' at least 2 can be bonded to respectively ring; M +for alkali metal ion.]
In formula, R c, Q 4, n, Y 1, R 3'～R 6', M +the same respectively.
As ammonium salt, can enumerate hydrochloride or the bromate etc. of abovementioned alkyl amine, dialkylamine, trialkylamine and aromatic amine.
About reacting of compound (1-13) and ammonium salt, can similarly implement with existing known salt method of replacing.For example, by water-soluble to compound (1-13) and ammonium salt, methylene chloride, acetonitrile, methyl alcohol, chloroform equal solvent, wait and make its reaction by stirring.
Temperature of reaction is preferably 0 DEG C～150 DEG C left and right, more preferably 0 DEG C～100 DEG C left and right.Reaction time according to reactivity and the temperature of reaction etc. of compound (1-13) and ammonium salt and different, is preferably 0.5～10 hour, more preferably 1～5 hour conventionally.
After reaction finishes, can separate the compound in reactant liquor (1-14), refine.Separate, refining can utilize existing known method, for example, wash, concentrate, solvent extraction, distillation, crystallization, recrystallization, chromatography etc., can use separately any in them, or two or more is used in combination.
In the present invention, compound (1-14) has N +(R 3') (R 4') (R 5') (R 6') as kation portion, owing to being insoluble in water, therefore can refine by washing.
The structure of the compound (1-14) obtaining can be passed through 1h-nuclear magnetic resonance (NMR) spectrometry, 13c-NMR spectrometry, 19the common Analytical Methods of Organic Compounds such as F-NMR spectrometry, infrared ray absorbing (IR) spectrometry, mass spectrum (MS) method, elemental microanalysis method, X ray crystal diffraction method are confirmed.
" purposes of compound (b0-1) "
As mentioned above, compound of the present invention (b0-1) is new compound, can as synthetic as anti-corrosion agent composition with the compound of acid agent particularly the intermediate when compound (b1-1) of the present invention's the 3rd mode use.
That is, compound (b0-1) is carried out to salt displacement, by (the N of kation portion of compound (b0-1) +(R 3) (R 4) (R 5) (R 6)) be replaced as the such as organic cation such as sulfonium cation, iodide ion of suitable kation portion and the compound that obtains can produce sour (sulfonic acid) by exposure.Described compound can be used as anti-corrosion agent composition acid agent and uses.
Compound of the present invention (b0-1) is as the intermediate in the time replacing by above-mentioned salt to manufacture acid agent compound, very useful., because kation portion is N +(R 3) (R 4) (R 5) (R 6), therefore can easily refine this compound by washing, can expect the raising of final product purity.If kation portion is alkali metal ion, refining this compound that can make of washing dissolves, and is difficult to refine by washing.
In addition, replacing by salt the compound being made by compound of the present invention (b0-1) can not only use as acid agent, and mix the photolithographic characteristics that contributes to improve anti-corrosion agent composition after anti-corrosion agent composition using this compound as acid agent, for example improve exploring degree while forming resist pattern, mask reappearance (such as mask linearity (mask linearity: マ ス Network リ ニ ア リ テ イ) etc.), exposure (EL) allowance, resist pattern form, depth of focus (DOF) etc.
EL holds nargin and refers to when change exposure is exposed, can be so that the size in specialized range forms the scope of the exposure of resist pattern with the deviation of target size, obtain the scope of the exposure of the resist pattern of faithful to mask pattern, the value that EL holds nargin is larger, the variable quantity of the pattern dimension producing with the variation of exposure is less, the appearance nargin of operation more improves, thereby preferably.
Infer and produce the reasons are as follows of above-mentioned effect.The negative ion portion that, replaces by salt the compound being made by above-claimed cpd (b0-1) has at " Y 1-SO 3-" skeleton on bonding have R x-Q 3-O-Q 2-structure.Therefore, compared with the fluoro-alkyl azochlorosulfonate acid ion in the past using as negative ion, polarity is large, sterically hindered large, becomes huge structure.By inference, compared with the negative ion portion of the existing acid agents such as nine fluorine fourth azochlorosulfonate acid ions, the intermolecular interaction that polarity causes greatly with and huge spatial structure can suppress chemically and physically this diffusion of negative ion portion (acid) in resist film.Therefore, the acid that suppresses exposure area generation is spread to unexposed area, thereby poor (the dissolving contrast) of the dissolubility to alkaline developer of unexposed area and exposure area improved, and takes this, and exploring degree and resist pattern form improve.
Y 1can there is substituent alkylidene and maybe can have compared with the alkyl chain of substituent fluoro alkylidene and perfluoroalkyl chain that for example carbon number is 6～10 hard-decomposed, its decomposability is good, can obtain and consider that the operability of the biosome property accumulated further improves this effect.
As an example of the compound as anti-corrosion agent composition acid agent that compound of the present invention (b0-1) is manufactured as intermediate, can enumerate aftermentioned compound of the present invention (b1-1).
" compound (b1-1) "
Then, the compound to the present invention's the 3rd mode (b1-1) describes.Compound (b1-1) preferably uses as the acid agent of the anti-corrosion agent composition of the present invention's the 1st mode.
R in formula (b1-1) x, Y 1, Q 2and Q 3respectively with above-mentioned general formula (b0-1) in R x, Y 1, Q 2and Q 3identical.
As Z +organic cation, the kation beyond the ion representing as long as above-mentioned general formula (w-1), is not particularly limited, and can suitably use in the past as the kation portion of salt acid agent and known kation.In described kation portion, as Z +organic cation, preferably sulfonium cation or iodide ion, particularly preferably sulfonium cation.
Particularly, can preferably use following general formula (b '-1), (b '-2), (b-5) or (b-6) the kation portion that represents.
[in formula, R 1"～R 3", R 5"～R 6" represent independently respectively aryl or alkyl; R 1"～R 3" in any 2 mutually bonding and with Cheng Huan together with sulphur atom in formula; R 1"～R 3" at least one represent aryl, R 5"～R 6" at least one represent aryl.]
[in formula, R 40hydrogen atom or alkyl, R 41alkyl, acetyl group, carboxyl or hydroxyalkyl, R 42～R 46be alkyl, acetyl group, alkoxy, carboxyl or hydroxyalkyl independently respectively; n 0～n 5be respectively 0～3 integer independently, wherein, n 0+ n 1be below 5, n 6it is 0～2 integer.]
In formula (b '-1), R 1"～R 3" represent independently respectively aryl or alkyl.R 1"～R 3" in any 2 mutually bonding and with Cheng Huan together with sulphur atom in formula.
And, R 1"～R 3" at least one represent aryl.R 1"～R 3" in preferably 2 be above aryl, most preferably R 1"～R 3" be all aryl.
As R 1"～R 3" aryl; be not particularly limited substituted aryl ,-(R after what can to enumerate such as carbon number be 6～20 replaced by alkyl, alkoxy, alkoxyalkyl oxygen base, alkoxy carbonyl alkyl oxygen base, halogen atom, hydroxyl etc. without the aryl replacing, this part or all hydrogen atom without the aryl replacing 4')-C (=O)-R 5'.R 4' be that carbon number is 1～5 alkylidene.R 5' be aryl.As R 5' aryl, can enumerate and above-mentioned R 1"～R 3" the identical group of aryl.
As the aryl without replacing, from viewpoint that can be cheap synthetic, the aryl that preferably carbon number is 6～10.Specifically can enumerate for example phenyl, naphthyl.
As the alkyl in substituted aryl, the alkyl that preferably carbon number is 1～5, most preferable, ethyl, propyl group, normal-butyl, the tert-butyl group.
As the alkoxy in substituted aryl, the alkoxy that preferably carbon number is 1～5, most preferably methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, tert-butoxy.
As the halogen atom in substituted aryl, preferably fluorine atom.
As the alkoxyalkyl oxygen base in substituted aryl, can enumerate for example general formula-O-C (R 47) (R 48)-O-R 49[in formula, R 47, R 48be respectively the alkyl of hydrogen atom or straight chain shape or a chain independently, R 49it is alkyl.] represent group.
R 47, R 48in, the carbon number of alkyl is preferably 1～5, can be straight chain shape, can be also a chain, preferably ethyl, methyl, most preferable.
R 47, R 48preferably at least one party is hydrogen atom.Particularly preferably a side is hydrogen atom, and the opposing party is hydrogen atom or methyl.
As R 49alkyl, preferably carbon number is 1～15, can be any in straight chain shape, a chain, ring-type.
As R 49in straight chain shape, the alkyl of chain, preferably carbon number is 1～5, can enumerate such as methyl, ethyl, propyl group, normal-butyl, the tert-butyl group etc.
As R 49in cyclic alkyl, preferably carbon number is 4～15, more preferably carbon number is 4～12, most preferably carbon number is 5～10.Specifically can enumerate by the alkyl of carbon number 1～5, fluorine atom or fluoro-alkyl replaces or the polynaphthene such as unsubstituted mononaphthene, dicyclo alkane, three cycloalkanes, tetracycloalkane is sloughed 1 group after above hydrogen atom etc.As mononaphthene, can enumerate cyclopentane, cyclohexane etc.As polynaphthene, can enumerate diamantane, norbornane, isoborneol alkane (isobornane), tristane, Fourth Ring dodecane etc.Wherein, preferably diamantane is sloughed more than 1 group after hydrogen atom.
As the alkoxy carbonyl alkyl oxygen base in substituted aryl, can enumerate for example general formula :-O-R 50-C (=O)-O-R 51[in formula, R 50the alkylidene of straight chain shape or a chain, R 51it is tertiary alkyl.] represent group.
As R 50in straight chain shape, the alkylidene of chain, preferably carbon number is 1～5, can enumerate for example methylene, ethylidene, trimethylene, tetramethylene, 1,1-dimethyl ethylidene etc.
As R 51in tertiary alkyl, can enumerate 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, 1-methyl isophthalic acid-cyclopentyl, 1-ethyl-1-cyclopentyl, 1-methyl isophthalic acid-cyclohexyl, 1-ethyl-1-cyclohexyl, 1-(1-adamantyl)-1-Methylethyl, 1-(1-adamantyl)-1-methyl-propyl, 1-(1-adamantyl)-1-methyl butyl, 1-(1-adamantyl)-1-methyl amyl; 1-(1-cyclopentyl)-1-Methylethyl, 1-(1-cyclopentyl)-1-methyl-propyl, 1-(1-cyclopentyl)-1-methyl butyl, 1-(1-cyclopentyl)-1-methyl amyl; 1-(1-cyclohexyl)-1-Methylethyl, 1-(1-cyclohexyl)-1-methyl-propyl, 1-(1-cyclohexyl)-1-methyl butyl, 1-(1-cyclohexyl)-1-methyl amyl, the tert-butyl group, tertiary pentyl, tertiary hexyl etc.
As R 1"～R 3" aryl, respectively preferred phenyl or naphthyl.
As R 1"～R 3" alkyl, be not particularly limited, can enumerate the alkyl of straight chain shape that such as carbon number is 1～10, a chain or ring-type etc.From the viewpoint of exploring degree excellence, preferably carbon number is 1～5.Specifically can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, n-pentyl, cyclopentyl, hexyl, cyclohexyl, nonyl, decyl etc.Wherein, from exploring degree excellence and the cheap synthetic viewpoint of energy, can preferable methyl.
Work as R 1"～R 3" in any 2 mutual bondings and in the time becoming to encircle together with sulphur atom in formula, be preferably formed and comprise sulphur atom in 3～10 interior rings, particularly preferably form 5～7 rings.
Work as R 1"～R 3" in any 2 mutual bondings and in the time becoming to encircle together with sulphur atom in formula, remaining one is preferably aryl.Above-mentioned aryl can be enumerated and above-mentioned R 1"～R 3" the identical group of aryl.
The object lesson of the kation portion representing as formula (b '-1), can enumerate triphenylsulfonium, (3,5-3,5-dimethylphenyl) diphenyl sulfonium, (4-(2-Buddha's warrior attendant alkoxy methyl oxygen base)-3,5-3,5-dimethylphenyl) diphenyl sulfonium, (4-(2-Buddha's warrior attendant alkoxy methyl oxygen base) phenyl) diphenyl sulfonium, (4-(tert-butoxycarbonyl methyl oxygen base) phenyl) diphenyl sulfonium, (4-(tert-butoxycarbonyl methyl oxygen base)-3,5-3,5-dimethylphenyl) diphenyl sulfonium, (4-(2-methyl-2-adamantyl oxygen base carbonyl methyl oxygen base) phenyl) diphenyl sulfonium, (4-(2-methyl-2-adamantyl oxygen base carbonyl methyl oxygen base)-3,5-3,5-dimethylphenyl) diphenyl sulfonium, three (4-aminomethyl phenyl) sulfonium, dimethyl (4-hydroxyl naphthyl) sulfonium, one phenyl dimethyl sulfonium, diphenyl monomethyl sulfonium, (4-aminomethyl phenyl) diphenyl sulfonium, (4-methoxyphenyl) diphenyl sulfonium, three (the 4-tert-butyl group) phenyl sulfonium, diphenyl (1-(4-methoxyl) naphthyl) sulfonium, two (1-naphthyl) phenyl sulfonium, 1-phenyl thiophane (phenyl tetrahydrothiophenium), 1-(4-aminomethyl phenyl) thiophane, 1-(3,5-dimethyl-4-hydroxyphenyl) thiophane, 1-(4-methoxynaphthalene-1-yl) thiophane, 1-(4-ethoxy naphthalene-1-yl) thiophane, 1-(4-n-butoxy naphthalene-1-yl) thiophane, 1-phenyl tetrahydric thiapyran, 1-(4-hydroxyphenyl) tetrahydric thiapyran, 1-(3,5-dimethyl-4-hydroxyphenyl) tetrahydric thiapyran, 1-(4-aminomethyl phenyl) tetrahydric thiapyran etc.
In formula (b '-2), R 5" and R 6" represent independently respectively aryl or alkyl.R 5" and R 6" at least one represent aryl.Preferably R 5" and R 6" both are aryl.
As R 5" and R 6" aryl, can enumerate and R 1"～R 3" the identical group of aryl.
As R 5" and R 6" alkyl, can enumerate and R 1"～R 3" the identical group of alkyl.
Wherein, R most preferably 5" and R 6" be phenyl.
The object lesson of the kation portion representing as formula (b '-2), can enumerate diphenyl iodine, two (4-tert-butyl-phenyl) iodine etc.
The R of general formula (b-5)～(b-6) 40～R 46in, the alkyl that the preferred carbon number of alkyl is 1～5, wherein, the more preferably alkyl of straight chain shape or a chain, particularly preferably methyl, ethyl, propyl group, isopropyl, normal-butyl or the tert-butyl group.
The alkoxy that the preferred carbon number of alkoxy is 1～5, the wherein more preferably alkoxy of straight or branched, particularly preferably methoxyl, ethoxy.
Group after one or more hydrogen atoms in the preferred abovementioned alkyl of hydroxyalkyl are replaced by hydroxyl, can enumerate methylol, hydroxyethyl, hydroxypropyl etc.
Work as OR 40with symbol n 0while being more than 2 integers, multiple OR 40can be identical or different respectively.
Work as R 41～R 46with symbol n 1～n 6while being more than 2 integers, multiple R 41～R 46can be identical or different respectively.
N 0be preferably 0 or 1.
N 1be preferably 0～2.
N 2and n 3be respectively preferably 0 or 1 independently, more preferably 0.
N 4be preferably 0～2, more preferably 0 or 1.
N 5be preferably 0 or 1, more preferably 0.
N 6be preferably 0 or 1.
As Z +preferred formula (b '-1) or (b-5) the kation portion of expression, the kation portion of particularly preferably following formula (b '-1-1)～(b '-1-10), (b-5-1)～(b-5-4) represent, the kation portion that the kation portion of the triphenyl skeletons such as the kation portion that more preferably formula (b '-1-1)～(b '-1-8) represents or (b '-1-10) represent.
Formula (b '-1-9)～(b '-1-10) in, R 8, R 9be 1～5 alkyl, alkoxy, hydroxyl for thering is substituent phenyl, naphthyl or carbon number independently respectively, preferably can there is substituent phenyl.
U is 1～3 integer, most preferably 1 or 2.
As compound (b1-1), the compound that preferred following general formula (b1-1-1) represents.
[in formula, R x, Y 1and Z +respectively with above-mentioned general formula (b1-1) in R x, Y 1and Z +identical; R 1for alkylidene.]
In above-mentioned general formula (b1-1-1), R x, Y 1and Z +respectively with above-mentioned general formula (b1-1) in R x, Y 1and Z +identical.
R 1alkylidene can be any in straight chain shape, chain, ring-type, preferably straight chain shape or a chain, further preferred straight chain shape.
The carbon number of the alkylidene of straight chain shape or chain is preferably 1～12, and more preferably 1～5, more preferably 1～3.As this alkylidene, specifically can enumerate for example methylene [CH 2-];-CH (CH 3)-,-CH (CH 2cH 3)-,-C (CH 3) 2-,-C (CH 3) (CH 2cH 3)-,-C (CH 3) (CH 2cH 2cH 3)-,-C (CH 2cH 3) 2-wait alkyl methylene; Ethylidene [CH 2cH 2-];-CH (CH 3) CH 2-,-CH (CH 3) CH (CH 3)-,-C (CH 3) 2cH 2-,-CH (CH 2cH 3) CH 2-wait alkyl ethylidene; Trimethylene (positive propylidene) [CH 2cH 2cH 2-];-CH (CH 3) CH 2cH 2-,-CH 2cH (CH 3) CH 2-wait alkyl trimethylene; Tetramethylene [CH 2cH 2cH 2cH 2-];-CH (CH 3) CH 2cH 2cH 2-,-CH 2cH (CH 3) CH 2cH 2-wait alkyl tetramethylene; Pentamethylene [CH 2cH 2cH 2cH 2cH 2-] etc.Wherein, preferred methylene, ethylidene or positive propylidene, particularly preferably ethylidene.
As compound (b1-1), particularly preferably following general formula (b1-1-11)～(b1-1-13) compound of expression.
[in formula, Z +the integer the same, p is 1～3, q1～q3 is respectively 1～12 integer independently, the integer that r1 is 0～3, the integer that g is 1～20, R 7for substituting group.]
As R 7substituting group, can be set forth in above-mentioned R xthe middle substituting group that can have as aliphatic alkyl and the identical group of group enumerated.
Work as R 7with symbol (r1) while being more than 2 integers, the multiple R in this compound 7can be identical or different respectively.
P is preferably 1 or 2.
Q1～q3 is respectively preferably 1～5 independently, more preferably 1～3.
R1 is preferably 0～2 integer, and more preferably 0 or 1.
G is more preferably 1～15, more preferably 1～10.
Compound of the present invention (b1-1) is new compound.
Compound of the present invention (b1-1) can use with acid agent as chemically amplified photoresist composition, can be used as acid agent and mixes in chemically amplified photoresist composition.
The manufacture method of compound of the present invention (b1-1) is not particularly limited, for example, can adopt the manufacture method of the compounds of this invention described later (b1-1) to manufacture.
" manufacture method of compound (b1-1) "
Then, the compound to the present invention's the 4th mode (b1-1) manufacture method describes.
Compound (b1-1) manufacture method of the present invention's the 4th mode comprises that the compound (b0-02) by making compound (b0-1) and following general formula (b0-02) expression that following general formula (b0-1) represents reacts to obtain the operation of compound (b1-1).
Z +A -...(b0-02)
[in formula, R xbe to there is substituent alkyl, but substituting group is not nitrogen-atoms; Q 2and Q 3be the linking group of singly-bound or divalent independently respectively; Y 1that carbon number is 1～4 alkylidene or fluoro alkylidene; W +it is the ion that alkali metal ion or following general formula (w-1) represent; Z +organic cation, but except the ion that following general formula (w-1) represents; A -it is non-nucleophilicity negative ion.]
[in formula, R 3～R 6maybe can there is substituent alkyl for hydrogen atom independently respectively, R 3～R 6in at least 1 be above-mentioned alkyl, R 3～R 6in at least 2 can be bonded to respectively ring.]
In formula, R x, Q 2, Q 3, Y 1, Z +respectively with above-mentioned general formula (b1-1) in R x, Q 2, Q 3, Y 1, Z +identical.
W +it is the ion (hereinafter referred to as substituted ammonium ion) that alkali metal ion or above-mentioned general formula (w-1) represent.
W +in, as alkali metal ion, can enumerate sodion, potassium ion, lithium ion etc.
In formula (W-1), R 3～R 6respectively with above-mentioned general formula (b0-1) in R 3～R 6identical.
A -it is non-nucleophilicity negative ion.
As this non-nucleophilicity ion, can enumerate the halogen such as bromide ion, chlorion ion such as, can form acid sour ion, BF lower than compound (b0-1) 4 -, AsF 6 -, SbF 6 -, PF 6 -or ClO 4 -deng.
As A -in can form the acid sour ion lower than compound (b0-1), can enumerate the azochlorosulfonate acid ions such as p-toluenesulfonic acid ion, methane-sulforic acid ion, benzene sulfonic acid ion, trifluoromethanesulfonic acid ion.
In compound (b1-1) manufacture method of the present invention's the 4th mode, particularly preferably compound (b0-1) is the compound (b0-1) that following general formula (b0-1) represents, compound (b1-1) is the compound (b1-1-1) that following general formula (b1-1-1) represents.
[in formula, R x, Y 1and W +with the R in above-mentioned general formula (b0-1) x, Y 1and W +identical; R bwith R xidentical; Z +with the Z in above-mentioned general formula (b1-1) +identical; R 1with the R in above-mentioned general formula (b0-1-11) 1identical.]
Above-claimed cpd (b0-01) for example can be by making the compound (1-3) that following general formula (1-3) represents react and synthesize with the compound (2-1) of following general formula (2-1) expression.
[in formula, R x, R 1, Y 1, W +the same respectively, X 22for halogen atom.]
As X 22halogen atom, can enumerate bromine atoms, chlorine atom, iodine atom, fluorine atom etc., from reactive excellent viewpoint, preferably bromine atoms or chlorine atom, particularly preferably chlorine atom.
Compound (1-3), (2-1) can use respectively commercially available product, also can synthesize.
For example,, as the W in compound (1-3) +during for alkali metal ion, the compound that represents as this compound (following general formula (1-3 ') (1-3 ')) preferred synthetic method, can enumerate the method with the operation by compound (1-1) that following general formula (1-1) represents is reacted obtain compound (1-3 ') with the compound (1-2) of following general formula (1-2) expression.
HO-R 1-O-R 2...(1-1)
[in formula, R 1, Y 1same as described above respectively, R 2for thering is aromatic series base as substituent fatty group, M +for alkali metal ion.]
As M +, can enumerate and above-mentioned W +the alkali metal ion that cited alkali metal ion is identical.
R 2for thering is aromatic series base as substituent fatty group.
This fatty group can be representative examples of saturated aliphatic base, can be also unsaturated aliphatic base.In addition, fatty group can be any in straight chain shape, a chain, ring-type, can be also their combination.
Fatty group can be the aliphatic alkyl only being formed by carbon atom and hydrogen atom, the part quilt that can be also the carbon atom of this aliphatic alkyl of formation contains the group after heteroatomic substituting group replaces, and can be also that part or all quilt that forms the hydrogen atom of this aliphatic alkyl contains the group after heteroatomic substituting group replacement.
As above-mentioned heteroatoms, as long as the atom beyond carbon atom and hydrogen atom, be not particularly limited, can enumerate such as halogen atom, oxygen atom, sulphur atom, nitrogen-atoms etc.As halogen atom, can enumerate fluorine atom, chlorine atom, iodine atom, bromine atoms etc.
Can only be formed by heteroatoms containing heteroatomic substituting group, can be also to contain group beyond heteroatoms or the group of atom.
As the substituting group of the part of alternate c atoms, specifically for example can enumerate-O-,-C (=O)-O-,-C (=O)-,-O-C (=O)-O-,-C (=O)-NH-,-NH-(H can be replaced by the substituting group such as alkyl, acyl group) ,-S-,-S (=O) 2-,-S (=O) 2-O-etc.In the time that fatty group contains cyclic group, can in the ring structure of this cyclic group, contain these substituting groups.
As part or all the substituting group that replaces hydrogen atom, specifically can enumerate for example alkoxy, halogen atom, haloalkyl, hydroxyl, oxygen atom (=O) ,-COOR 96,-OC (=O) R 97, cyano group etc.
As above-mentioned alkoxy, the alkoxy that preferably carbon number is 1～5, further preferred methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, tert-butoxy, most preferably methoxyl, ethoxy.
As above-mentioned halogen atom, can enumerate fluorine atom, chlorine atom, bromine atoms, iodine atom etc., preferably fluorine atom.
As above-mentioned haloalkyl, the group after part or all of hydrogen atom that can enumerate carbon number and be the alkyl such as 1～5 alkyl such as methyl, ethyl, propyl group, normal-butyl, the tert-butyl group replaced by above-mentioned halogen atom.
R 96and R 97be respectively straight chain shape, chain or the cyclic alkyl that hydrogen atom or carbon number are 1～15 independently.
Work as R 96and R 97in alkyl while being straight chain shape or chain, its carbon number is preferably 1～10, more preferably 1～5, more preferably 1 or 2.Specifically can enumerate the group identical with 1 valency saturated hydrocarbyl of straight chain shape described later or a chain.
Work as R 96and R 97in alkyl while being ring-type, this ring can be monocycle, can be also many rings.Its carbon number is preferably 3～15, and more preferably 4～12, more preferably 5～10.Specifically can enumerate the group identical with 1 valency saturated hydrocarbyl of ring-type described later.
As aliphatic alkyl, the straight chain shape that preferably carbon number is 1～30 or the saturated hydrocarbyl of a chain, straight chain shape or 1 valency unsaturated alkyl of chain or the aliphatic alkyl (alicyclic group) of the ring-type that carbon number is 3～30 that carbon number is 2～10.
As the saturated hydrocarbyl of straight chain shape, preferably carbon number is 1～20, more preferably 1～15, most preferably be 1～10.Specifically can enumerate such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, myristyl, pentadecyl, cetyl, isocetyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl etc.
As the saturated hydrocarbyl of chain, preferably carbon number is 3～20, more preferably 3～15, most preferably be 3～10.Specifically can enumerate such as 1-Methylethyl, 1-methyl-propyl, 2-methyl-propyl, 1-methyl butyl, 2-methyl butyl, 3-methyl butyl, 1-ethyl-butyl, 2-ethyl-butyl, 1-methyl amyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl etc.
As unsaturated alkyl, preferably carbon number is 2～5, more preferably 2～4, more preferably 3.As 1 valency unsaturated alkyl of straight chain shape, can enumerate such as vinyl, propenyl (allyl), butenyl group etc.As 1 valency unsaturated alkyl of a chain, can enumerate such as 1-methylpropenyl, 2-methylpropenyl etc.
Propenyl particularly preferably in above-mentioned unsaturated alkyl.
As alicyclic group, can be monocycle base, can be also many cyclic groups.Its carbon number is preferably 3～30, and more preferably 5～30, more preferably 5～20, be particularly preferably 6～15, most preferably be 6～12.For example specifically can enumerate and remove more than 1 group after hydrogen atom by mononaphthene; Remove more than 1 group after hydrogen atom etc. by polynaphthenes such as dicyclo alkane, three cycloalkanes, tetracycloalkanes.More specifically, for example can enumerate and remove more than 1 group after hydrogen atom by the mononaphthene such as cyclopentane, cyclohexane; Remove more than 1 group after hydrogen atom etc. by polynaphthenes such as diamantane, norbornane, isoborneol alkane, tristane, Fourth Ring decane.
At R 2in, above-mentioned fatty group can have aromatic series base as substituting group.
As aromatic series base, can enumerate phenyl, biphenyl (biphenyl) base, fluorenes (fluorenyl) base, naphthyl, anthracene (anthryl) base, phenanthryl etc. and remove 1 aryl after hydrogen atom by aromatic hydrocarbon ring; Heteroaryl after a part that forms the carbon atom of the ring of these aryl is replaced by the heteroatoms such as oxygen atom, sulphur atom, nitrogen-atoms etc.
It is the substituting groups such as 1～10 alkyl, haloalkyl, alkoxy, hydroxyl, halogen atom that these aromatic series bases can have carbon number.The preferred carbon number of alkyl in this substituting group or haloalkyl is 1～8, and more preferably carbon number is 1～4.This haloalkyl is preferably fluoro-alkyl.This halogen atom can be enumerated fluorine atom, chlorine atom, iodine atom, bromine atoms etc., preferably fluorine atom.
In addition, if the R in compound (1-1) 2for aromatic series base, with R 2adjacent oxygen atom does not pass through fatty group and direct and aromatic rings bonding, and compound (1-1) cannot carry out with reacting of compound (1-2), can not get compound (1-3).
Compound (1-1), (1-2) can use respectively commercially available product, also can utilize known method to synthesize.
For example compound (1-2), can enumerate and comprise that the compound (0-1) by following general formula (0-1) is represented heat, neutralize and obtain the operation (hereinafter referred to as salt formation operation) of the compound (0-2) that following general formula (0-2) represents and by above-claimed cpd (0-2) is heated to the method for the operation (hereinafter referred to as carboxylic acidizing process) that obtains compound (1-2) under higher than the sour existence of compound (1-2) in acid strength under the existence of alkali.
[in formula, R 01for alkyl, Y 1, M +the same.]
As R 01alkyl, preferably the alkyl of straight chain shape or a chain, specifically can enumerate methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl, the tert-butyl group, amyl group, isopentyl, neopentyl etc.Wherein, the alkyl that preferably carbon number is 1～4, most preferable.
As compound (0-1), can use commercially available product.
Form operation about salt, for example can be by compound (0-1) being dissolved, is added in solvent alkali in this solution, heating and implement.
As solvent, as long as the solvent of energy dissolved compound (0-1), can enumerate such as water, tetrahydrofuran etc.
As alkali, use the alkali corresponding with M in formula (0-2), as this alkali, can enumerate the alkali metal hydroxides such as NaOH, potassium hydroxide, lithium hydroxide.
About the consumption of alkali, with respect to 1 mole of compound (0-1), be preferably 1～5 mole, more preferably 2～4 moles.
Heating-up temperature is preferably 20～120 DEG C of left and right, more preferably 50～100 DEG C of left and right.Heat time is according to heating-up temperature etc. and different, and preferably 0.5～12 hour conventionally, further preferably 1～5 hour.
About the neutralization after above-mentioned heating, can implement by adding the acid such as hydrochloric acid, sulfuric acid, p-toluenesulfonic acid in the reactant liquor after above-mentioned heating.
Now, preferably make the pH (25 DEG C) of reactant liquor after acid is added 6～8 implement neutralization.In and time the temperature of reactant liquor be preferably 20～30 DEG C, more preferably 23～27 DEG C.
After reaction finishes, can separate the compound in reactant liquor (0-2), refine.Separate, refining can utilize existing known method, for example concentrated, solvent extraction, distillation, crystallization, recrystallization, chromatography etc., can use separately any in them, or two or more is used in combination.
In carboxylic acidizing process, by by form at above-mentioned salt the compound (0-2) that obtains in operation acid strength higher than the sour existence of compound (1-2) under heating obtain this compound (1-2).
" acid strength is higher than the acid (below sometimes referred to as strong acid) of compound (1-2) " refers to the acid of be less than in compound (1-2)-COOH of the value of pKa (25 DEG C).By using described strong acid, in compound (0-2)-COO -m +become-COOH, obtain compound (1-2).
As strong acid, the suitably acid of the pKa of be less than in above-claimed cpd (1-2)-COOH of choice for use pKa from known acid.In compound (1-2)-pKa of COOH can try to achieve by known titrimetry.
As strong acid, specifically can enumerate the sulfonic acid such as aryl sulfonic acid, alkyl sulfonic acid, sulfuric acid, hydrochloric acid etc.As aryl sulfonic acid, can enumerate for example p-toluenesulfonic acid.As alkyl sulfonic acid, can enumerate such as methane-sulforic acid, trifluoromethanesulfonic acid etc.As strong acid, from the viewpoint of the dissolubility to organic solvent and refining easiness, particularly preferably p-toluenesulfonic acid.
About carboxylic acidizing process, for example can be by compound (0-2) be dissolved in solvent, add after strong acid and heat and implement.
As solvent, as long as the solvent of energy dissolved compound (0-2), can enumerate such as acetonitrile, MEK etc.
About the consumption of strong acid, with respect to 1 mole of compound (0-2), be preferably 0.5～3 mole, more preferably 1～2 mole.
Heating-up temperature is preferably 20～150 DEG C of left and right, more preferably 50～120 DEG C of left and right.Heat time is according to heating-up temperature etc. and different, and preferably 0.5～12 hour conventionally, further preferably 1～5 hour.
After reaction finishes, can separate the compound in reactant liquor (1-2), refine.Separate, refining can utilize existing known method, for example concentrated, solvent extraction, distillation, crystallization, recrystallization, chromatography etc., can use separately any in them, or two or more is used in combination.
For example,, as the W in compound (1-3) +during for above-mentioned substituted ammonium ion, compound that this compound (following general formula (1-3 ") represents (1-3 ")) for example can be by making above-claimed cpd (1-3 ') react to manufacture with ammonium salt.
[in formula, R x, R 1, Y 1, R 3～R 6same as described above respectively.]
As the ammonium salt now using, can enumerate hydrochloride or the bromate etc. of abovementioned alkyl amine, dialkylamine, trialkylamine and aromatic amine.
About reaction, for example, compound (1-3 ') can be dissolved in water, methylene chloride, acetonitrile, methyl alcohol, chloroform equal solvent with ammonium salt and by stirring etc., it be reacted.
Temperature of reaction is preferably 0 DEG C～150 DEG C left and right, more preferably 0 DEG C～100 DEG C.Reaction time according to reactivity and the temperature of reaction etc. of compound (1-3 '), ammonium salt and different, is preferably 0.5～10 hour, more preferably 1～5 hour conventionally.
As making compound (1-3) and the method that compound (2-1) reacts, be not particularly limited, can enumerate the method that for example makes compound (1-3) contact with compound (2-1) in reaction dissolvent.The method for example can be by adding compound (2-1) in the solution that compound (1-3) obtains and implement to being dissolved with in reaction dissolvent under the existence of alkali.
As reaction dissolvent, as long as dissolving compound (1-3) as raw material and the solvent of compound (2-1), specifically can enumerate tetrahydrofuran (THF), acetone, dimethyl formamide (DMF), dimethyl acetamide, dimethyl sulfoxide (DMSO) (DMSO), acetonitrile etc.
As alkali, can enumerate the organic bases such as such as triethylamine, 4-dimethylaminopyridine (DMAP), pyridine; NaOH, K 2cO 3, Cs 2cO 3deng inorganic base etc.
About the addition of compound (2-1), with respect to compound (1-3), be preferably about 1～3 equivalent, more preferably 1～2 equivalent.
Temperature of reaction is preferably-20～40 DEG C, more preferably 0～30 DEG C.Reaction time according to reactivity and the temperature of reaction etc. of compound (1-3) and compound (2-1) and different, is preferably 1～120 hour, more preferably 1～48 hour conventionally.
As the W in compound (b0-01) +during for above-mentioned substituted ammonium ion, compound that this compound (following general formula (b0-01 ') represents (b0-01 ')) for example can be by above-claimed cpd (1-3 '), above-claimed cpd (2-1) be manufactured with the method for amine or ammonium salt simultaneous reactions.
[in formula, R x, R 1, Y 1, W +, X 22same as described above respectively.]
Above-claimed cpd (1-3 '), above-claimed cpd (2-1) can similarly react with the situation that above-claimed cpd (2-1) reacts with above-claimed cpd (1-3) with amine or ammonium salt.
As the amine now using, can enumerate abovementioned alkyl amine, dialkylamine, trialkylamine and aromatic amine etc., as ammonium salt, can enumerate the tetra-alkyl ammonium hydroxides (as the alkyl in tetra-allkylammonium, the alkyl that is 1～4 for carbon number independently respectively) such as Tetramethylammonium hydroxide, tetraethyl oxyammonia, tetrabutylammonium hydroxide amine.
In above-mentioned manufacture method, the intermediate of the substituted ammonium salts such as above-claimed cpd (1-3 "), compound (b0-01 ') when manufacturing compound of the present invention (b1-1) is very useful., because kation portion is N +(R 3) (R 4) (R 5) (R 6), therefore can easily refine this compound by washing, can expect the raising of final product purity.If kation portion is alkali metal ion, refining this compound that can make of washing dissolves, and is difficult to refine by washing.
Therefore,, in manufacture method of the present invention, the intermediate that compound (b1-1) preferably has an above-mentioned substituted ammonium ion by kation portion is manufactured.
Compound (b0-01) can similarly be implemented with existing known salt method of replacing with reacting of compound (b0-02).For example, compound (b0-01) and compound (b0-02) can be dissolved in water, methylene chloride, acetonitrile, methyl alcohol, chloroform equal solvent, wait and make its reaction by stirring.
Temperature of reaction is preferably 0 DEG C～150 DEG C left and right, more preferably 0 DEG C～100 DEG C left and right.Reaction time is according to reactivity and the temperature of reaction etc. of compound (b0-01) and compound (b0-02) and different, and preferably 0.5～12 hour conventionally, further preferably 1～5 hour.
After reaction finishes, can separate the compound in reactant liquor (b1-1), refine.Separate, refining can utilize existing known method, for example concentrated, solvent extraction, distillation, crystallization, recrystallization, chromatography etc., can use separately any in them, or two or more is used in combination.
The structure of the compound (b1-1) obtaining can be passed through 1h-nuclear magnetic resonance (NMR) spectrometry,
13c-NMR spectrometry, 19the general Analytical Methods of Organic Compounds such as F-NMR spectrometry, infrared ray absorbing (IR) spectrometry, mass spectrum (MS) method, elemental microanalysis method, X ray crystal diffraction method are confirmed.
" acid agent "
The acid agent of the present invention's the 5th mode is formed by the compound (b1-1) of the invention described above.
This acid agent is chemically amplified photoresist composition acid agent, for example can be as the acid agent composition (B) of the anti-corrosion agent composition of aftermentioned the present invention the 1st mode.
The compound that this acid agent is particularly preferably represented by following general formula (b1-1-1) forms.
" anti-corrosion agent composition "
Then, the anti-corrosion agent composition of the present invention's the 1st mode is described.
The anti-corrosion agent composition of the present invention's the 1st mode contains under sour effect base material component (A) (hereinafter referred to as (A) composition) that the dissolubility of alkaline developer is changed and by exposing to acidic acid agent composition (B) (hereinafter referred to as (B) composition).
About the resist film that uses described anti-corrosion agent composition to form, if optionally expose, produce acid by (B) composition in the time that resist pattern forms, this acid makes (A) composition change to the dissolubility of alkaline developer.Consequently, the exposure portion of this resist film changes the dissolubility of alkaline developer, and unexposed portion is constant to the dissolubility of alkaline developer, therefore develops by alkali, and dissolved the removing of unexposed portion when exposure portion when eurymeric, minus, forms resist pattern.
Anti-corrosion agent composition of the present invention can be negative resist composition, can be also eurymeric anti-corrosion agent composition.
< (A) composition >
As (A) composition, conventionally can use separately the organic compound of a kind of base material component of using as chemically amplified photoresist or two or more mixing to use.
Here, " base material component " refers to the organic compound with film forming ability, and preferably using molecular weight is more than 500 organic compounds.Because the molecular weight of this organic compound is more than 500, therefore film forming ability improves, and easily forms the resist pattern of nanometer level.
Above-mentioned molecular weight be more than 500 organic compounds can roughly be divided into molecular weight at the low molecular weight organic compound of 500 above less thaies 2000 (hereinafter referred to as low molecular compound.) and the high molecular weight resin (macromolecular material) of molecular weight more than 2000.As above-mentioned low molecular compound, conventionally adopt non-polymer.In the situation of resin (polymkeric substance, multipolymer), as " molecular weight ", adopt the matter average molecular weight of the polystyrene conversion recording by GPC (gel permeation chromatography).During hereinafter to be referred as " resin ", refer to the resin of molecular weight more than 2000.
As (A) composition, can use the resin that alkali dissolubility changes under sour effect, also can use the low molecular material that alkali dissolubility changes under sour effect.
In the time that anti-corrosion agent composition of the present invention is negative resist composition, as (A) composition, can adopt soluble base material component in alkaline developer, in this negative resist composition, also mix crosslinking chemical.
About described negative resist composition, in the time producing acid by exposure by (B) composition, under the effect of this acid, between base material component and crosslinking chemical, generation is crosslinked, becomes indissoluble in alkaline developer.Therefore, in the formation of resist pattern, when the resist film obtaining be coated with this negative resist composition on substrate carries out selectivity exposure, exposure portion becomes indissoluble in alkaline developer, and unexposed portion is still solvable and do not change in alkaline developer, therefore can develop to form resist pattern by alkali.
As (A) composition of negative resist composition, conventionally use in alkaline developer soluble resin (hereinafter referred to as alkali soluble resin.)。
As alkali soluble resin, have by the resin that is selected from least one the derivative unit in α-(hydroxyalkyl) acrylic acid or α-(hydroxyalkyl) acrylic acid lower alkyl esters and can form the good resist pattern that swelling is few, therefore preferably.In addition, α-(hydroxyalkyl) acrylic acid refer to the carbon atom of the α position of carboxyl bonding on bonding have bonding on the acrylic acid of hydrogen atom and this α position carbon atom to have one or both in the alpha-hydroxyalkyl acrylic acid of hydroxyalkyl (the preferably hydroxyalkyl of carbon number 1～5).
As crosslinking chemical, if for example common employing has the amino crosslinking chemicals such as the glycoluril of methylol or alkoxy methyl, can form the good resist pattern that swelling is few, therefore preferably.The blending amount of crosslinking chemical is preferably 1～50 mass parts with respect to alkali soluble resin 100 mass parts.
In the time that anti-corrosion agent composition of the present invention is eurymeric anti-corrosion agent composition, as (A) composition, adopt the base material component that the dissolubility in alkaline developer increases under sour effect.Should before exposure, be insoluble in alkaline developer by (A) composition, in the time producing acid by exposure by above-mentioned (B) composition, under the effect of this acid, the dissolubility in alkaline developer increases.Therefore, in the formation of resist pattern, if the resist film obtaining be coated with this eurymeric anti-corrosion agent composition on substrate carries out selectivity exposure, the dissolubility of exposure portion in alkaline developer changes to solubility from slightly solubility, and unexposed portion does not change, be still alkali slightly solubility, therefore can develop to form resist pattern by alkali.
In anti-corrosion agent composition of the present invention, (A) composition is preferably the base material component that the dissolubility in alkaline developer increases under sour effect., the preferred eurymeric anti-corrosion agent composition of anti-corrosion agent composition of the present invention.
Should (A) composition can be that the resinous principle (A1) that the dissolubility in alkaline developer increases under sour effect (is sometimes referred to as (A1) composition below.), can be also that the low molecular compound (A2) that the dissolubility in alkaline developer increases under sour effect (is sometimes referred to as (A2) composition below.), can be also their potpourri.Wherein, should preferably contain (A1) composition by (A) composition.
[(A1) composition]
As (A1) composition, conventionally, can use separately the resinous principle (substrate resin) of a kind of base material component of using as chemically amplified photoresist or two or more mixing to use.
In the manner, as (A1) composition, preferably contain the structural unit being derived by acrylate.
Here, in the present specification and claims, " structural unit being derived by acrylate " refers to the structural unit that the olefinic double bond fracture of acrylate forms.
" acrylate " the acrylate of hydrogen bonding atom, also comprises the carbon atom of α position and the acrylate of substituting group (atom or group beyond hydrogen atom) bonding on the carbon atom of α position.As substituting group, can enumerate low alkyl group, junior alkyl halides etc.
In addition, in the situation that there is no specified otherwise, the α position of the structural unit being derived by acrylate (carbon atom of α position) refers to the carbon atom with carbonyl bonding.
In acrylate, about the substituent low alkyl group as α position, specifically can enumerate the alkyl of the lower straight shapes such as methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl, the tert-butyl group, amyl group, isopentyl, neopentyl or a chain.
As junior alkyl halides, the group after part or all hydrogen atom that specifically can enumerate above-mentioned " the substituent low alkyl group of α position " is replaced by halogen atom.As this halogen atom, can enumerate fluorine atom, chlorine atom, bromine atoms, iodine atom etc., particularly preferably fluorine atom.
In the present invention, the preferred hydrogen atom of group, low alkyl group or junior alkyl halides with the α position bonding of acrylate, more preferably hydrogen atom, low alkyl group or fluoro low alkyl group, from the viewpoint of the industrial easiness obtaining, most preferably hydrogen atom or methyl.
(A1) composition particularly preferably has structural unit (a1) derivative by the acrylate that contains acid dissociation dissolution inhibition base and that come.
(A1) composition, except structural unit (a1), also preferably has by the derivative and next structural unit (a2) of acrylate containing containing the cyclic group of lactone.
(A1) composition is except structural unit (a1) or structural unit (a1) with (a2), also preferably has by containing the derivative and structural unit (a3) that comes of acrylate containing polar group aliphatic alkyl.
Structural unit (a1)
Acid dissociation dissolution inhibition base in structural unit (a1) has the alkali dissolution inhibition that makes (A1) composition entirety indissoluble in alkaline developer before dissociating, and under sour effect, dissociate and the dissolubility of this (A1) composition entirety in alkaline developer increased, can use the acid dissociation dissolution inhibition base of the chemically amplified photoresist substrate resin proposing up to now.Well-known have with (methyl) acrylic acid etc. in carboxyl form the group of the tertiary alkyl ester of ring-type or chain; The acetal type acid dissociation dissolution inhibition bases such as alkoxyalkyl etc.
Here, " tertiary alkyl ester " refers to: the hydrogen atom of carboxyl is replaced and formation ester by the alkyl of chain or ring-type, the structure of the oxygen atom of end of its ketonic oxygen base (C (O)-O-) and the tertiary carbon atom bonding of the alkyl of above-mentioned chain or ring-type.This tertiary alkyl ester under sour effect, the bond rupture between oxygen atom and tertiary carbon atom.
In addition, the alkyl of above-mentioned chain or ring-type can have substituting group.
Below, for simplicity, will be called " tertiary alkyl ester type acid dissociation dissolution inhibition base " by forming with carboxyl the group that tertiary alkyl ester has an acid dissociation.
As tertiary alkyl ester type acid dissociation dissolution inhibition base, can enumerate the acid dissociation dissolution inhibition base that aliphatics is propped up chain acid dissociation dissolution inhibition base, contained alicyclic group.
" aliphatics is propped up chain " refers to a chain structure without aromaticity.
The structure of " aliphatics is propped up chain acid dissociation dissolution inhibition base " is not limited to the group (alkyl) being formed by carbon and hydrogen, but preferred alkyl.In addition, " alkyl " can be saturated also can be unsaturated, conventionally preferably saturated.
Prop up chain acid dissociation dissolution inhibition base as aliphatics, preferably the tertiary alkyl of carbon number 4～8, specifically can enumerate the tert-butyl group, tertiary pentyl, tertiary heptyl etc.
" alicyclic group " refers to monocycle base or many cyclic groups without aromaticity.
" alicyclic group " in structural unit (a1) can have substituting group, also can there is no substituting group.As substituting group, can enumerate fluoro low alkyl group, the oxygen atom (=O) etc. of low alkyl group, the fluorine atom of carbon number 1～5, carbon number 1～5 after being replaced by fluorine atom.
The basic ring structure that " alicyclic group " removed after substituting group is not limited to the group (alkyl) being formed by carbon and hydrogen, but preferred alkyl.In addition, " alkyl " can be saturated also can be unsaturated, conventionally preferably saturated." alicyclic group " preferred many cyclic groups.
As alicyclic group, for example can enumerate replaced by low alkyl group, fluorine atom or fluoro-alkyl or the polynaphthene such as unsubstituted mononaphthene, dicyclo alkane, three cycloalkanes, tetracycloalkane remove more than 1 group after hydrogen atom etc.More specifically, can enumerate the polynaphthenes such as the mononaphthene such as cyclopentane, cyclohexane or diamantane, norbornane, isoborneol alkane, tristane, Fourth Ring decane and remove more than 1 group after hydrogen atom etc.
As the acid dissociation dissolution inhibition base that contains alicyclic group, for example can enumerate the group on the ring skeleton of the alkyl of ring-type with tertiary carbon atom, specifically can enumerate 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl etc.Or, can be listed below the group of stating in the structural unit that general formula (a1 "-1)～(a1 "-6) represent with the oxygen atom bonding of ketonic oxygen base (C (O)-O-) such, there is the alicyclic groups such as adamantyl, cyclohexyl, cyclopentyl, norborneol alkyl, tristane base, Fourth Ring dodecyl and the group with the chain alkylidene with tertiary carbon atom of its bonding.
[in formula, R represents hydrogen atom, low alkyl group or junior alkyl halides; R 15, R 16represent alkyl (any in straight chain shape, a chain, preferably carbon number is 1～5).]
In general formula (a1 "-1)～(a1 "-6), the low alkyl group of R or junior alkyl halides with above-mentioned can be identical with low alkyl group or the junior alkyl halides of the α position bonding of acrylate.
" acetal type acid dissociation dissolution inhibition base " conventionally with the hydrogen atom replacement of the alkali-soluble group end such as carboxyl, hydroxyl with oxygen atom bonding.In the time producing acid by exposing, under the effect of this acid, the bond rupture between acetal type acid dissociation dissolution inhibition base and the oxygen atom of this acetal type acid dissociation dissolution inhibition base institute bonding.
As acetal type acid dissociation dissolution inhibition base, can enumerate the group that for example following general formula (p1) represents.
[in formula, R 1', R 2' representing independently respectively hydrogen atom or low alkyl group, n represents 0～3 integer, Y represents low alkyl group or alicyclic group.]
In above-mentioned formula, n is preferably 0～2 integer, and more preferably 0 or 1, most preferably 0.
As R 1', R 2' low alkyl group, can enumerate the group identical with the low alkyl group of above-mentioned R, preferable methyl or ethyl, most preferable.
In the present invention, preferred R 1', R 2' at least one be hydrogen atom., acid dissociation dissolution inhibition base (p1) is preferably the group that following general formula (p1-1) represents.
[in formula, R 1', n, Y be same as described above.]
As the low alkyl group of Y, can enumerate the group identical with the low alkyl group of above-mentioned R.
As the alicyclic group of Y, can be from existing ArF resist etc. suitably choice for use, for example group identical with above-mentioned " alicyclic group " in a large amount of monocycles of proposing or polycycle alicyclic group.
As acetal type acid dissociation dissolution inhibition base, can also enumerate the group that following general formula (p2) represents.
[in formula, R 17, R 18independent is respectively alkyl or the hydrogen atom of straight chain shape or a chain, R 19it is the alkyl of straight chain shape, a chain or ring-type.R 17and R 19can distinguish is the alkylidene of straight chain shape or a chain independently, R 17end and R 19end can be bonded to ring.]
R 17, R 18in, the carbon number of alkyl is preferably 1～15, can be any in straight chain shape, a chain, preferably ethyl, methyl, most preferable.
Particularly preferably R 17, R 18in a side be hydrogen atom, the opposing party is methyl.
R 19be the alkyl of straight chain shape, a chain or ring-type, carbon number is preferably 1～15, can be any in straight chain shape, a chain or ring-type.
Work as R 19while being straight chain shape, chain, carbon number is preferably 1～5, more preferably ethyl, methyl, particularly preferably ethyl.
Work as R 19during for ring-type, carbon number is preferably 4～15, carbon number more preferably 4～12, and carbon number most preferably is 5～10.Particularly, can enumerate and be replaced by fluorine atom or fluoro-alkyl or the polynaphthene such as unsubstituted mononaphthene, dicyclo alkane, three cycloalkanes, tetracycloalkane is removed more than 1 group after hydrogen atom etc.Specifically can enumerate the polynaphthenes such as the mononaphthene such as cyclopentane, cyclohexane or diamantane, norbornane, isoborneol alkane, tristane, Fourth Ring dodecane and remove more than 1 group after hydrogen atom etc.Wherein, preferably diamantane is removed more than 1 group after hydrogen atom.
In addition, in above-mentioned formula, R 17and R 19can distinguish the alkylidene (alkylidene that preferably carbon number is 1～5) for straight chain shape or a chain independently, and R 19end and R 17end bonding.
Now, by R 17and R 19, R 19oxygen atom, this oxygen atom and the R of institute's bonding 17the carbon atom of institute's bonding forms cyclic group.As this cyclic group, preferably 4～7 rings, more preferably 4～6 rings.As the object lesson of this cyclic group, can enumerate THP trtrahydropyranyl, tetrahydrofuran base etc.
As structural unit (a1), preferably use be selected from the structural unit that structural unit that following general formula (a1-0-1) represents and following general formula (a1-0-2) represent more than a kind.
[in formula, R represents hydrogen atom, low alkyl group or junior alkyl halides; X 1represent acid dissociation dissolution inhibition base.]
[in formula, R represents hydrogen atom, low alkyl group or junior alkyl halides; X 2represent acid dissociation dissolution inhibition base; Y 2represent alkylidene, alicyclic group or there is the divalent linking group of ehter bond.]
In general formula (a1-0-1), the low alkyl group of R or junior alkyl halides with above-mentioned can be identical with low alkyl group or the junior alkyl halides of the α position bonding of acrylate.
X 1as long as acid dissociation dissolution inhibition base, be not particularly limited, can enumerate such as above-mentioned tertiary alkyl ester type acid dissociation dissolution inhibition base, acetal type acid dissociation dissolution inhibition base etc., preferred tertiary Arrcostab type acid dissociation dissolution inhibition base.
In general formula (a1-0-2), R is same as described above.
X 2with the X in formula (a1-0-1) 1identical.
Y 2for alkylidene, alicyclic group or there is the divalent linking group of ehter bond.
Work as Y 2while being alkylidene, the alkylidene that preferably carbon number is 1～10, more preferably carbon number is 1～6, and particularly preferably carbon number is 1～4, and most preferably carbon number is 1～3.
Work as Y 2while being alicyclic group, the preferably alicyclic group of divalent as this alicyclic group, can use the group identical with the group of explanation in above-mentioned " alicyclic group " except using the group of sloughing more than 2 hydrogen atom.
Work as Y 2while being the alicyclic group of divalent, particularly preferably remove more than 2 group after hydrogen atom by cyclopentane, cyclohexane, norbornane, isoborneol alkane, diamantane, tristane, Fourth Ring dodecane.
Work as Y 2, while thering is the divalent linking group of ehter bond, to be preferably-Y a-O-Y bthe group of-expression.
At above-mentioned-Y a-O-Y bin the group of-expression, Y athat can to have substituent carbon number be more than 2 divalent alkyl.Alkyl can be aliphatic alkyl, can be also aromatic hydrocarbyl.Preferred aliphat alkyl.As aliphatic alkyl, can enumerate the aliphatic alkyl that contains ring in the aliphatic alkyl, structure of straight chain shape or chain etc.Particularly, with Y 2while being divalent alicyclic group or Y 2in the group of enumerating while being alkylidene, carbon number is that more than 2 group is identical.In addition, Y acan there is substituting group, as this substituting group, work as Y afluoro low alkyl group, oxygen atom (=O) etc. that the carbon number that can enumerate fluorine atom while being the aliphatic alkyl of chain, is replaced by fluorine atom is 1～5, work as Y awhile containing the aliphatic alkyl of ring in structure, identical with the substituting group in above-mentioned " alicyclic group ".
As Y a, the preferably aliphatic alkyl of straight chain shape, the alkylidene of further preferred straight chain shape, the alkylidene of the straight chain shape that more preferably carbon number is 2～5, most preferably ethylidene.
Y bthat can to have substituent carbon number be more than 1 divalent alkyl.As Y balkyl, can enumerate and above-mentioned Y ain to enumerate the same carbon number of alkyl be more than 2 divalent alkyl and can have substituent methylene.The substituting group that can have as methylene, can enumerate the identical group of substituting group of enumerating with the substituting group that can have as above-mentioned chain aliphatic alkyl.
As Y b, the preferably aliphatic alkyl of straight chain shape or a chain, particularly preferably methylene or alkyl methylene.
The straight chain-like alkyl that the preferred carbon number of alkyl in alkyl methylene is 1～5, further preferably carbon number is 1～3 straight chain-like alkyl, most preferable.
As structural unit (a1), more specifically, can enumerate following general formula (a1-1)～(a1-4) structural unit of expression.
[in formula, X ' represents tertiary alkyl ester type acid dissociation dissolution inhibition base, and Y represents that carbon number is 1～5 low alkyl group or alicyclic group; N represents 0～3 integer; Y 2represent alkylidene, alicyclic group or there is the divalent linking group of ehter bond; R is same as described above, R 1', R 2' represent independently that respectively hydrogen atom or carbon number are 1～5 low alkyl group.]
In formula, X ' can enumerate and above-mentioned X 1in the identical group of illustrative tertiary alkyl ester type acid dissociation dissolution inhibition base.
As R 1', R 2', n, Y, respectively with the general formula (p1) described in above-mentioned " dissociating property of acetal type dissolution inhibition base " in R 1', R 2', n, Y be identical.
As Y 2, can enumerate with above-mentioned general formula (a1-0-2) in Y 2identical group.
Below, enumerate above-mentioned general formula (a1-1)～(a1-4) object lesson of the structural unit of expression.
As structural unit (a1), can use separately a kind, also can two or more be used in combination.
Wherein, the structural unit that preferred formula (a1-1) represents, particularly, more preferably use at least a kind that is selected from (a1-1-1)～(a1-1-6), (a1-1-17)～(a1-1-18), (a1-1-35)～(a1-1-41) and (a1-3-49)～(a1-3-50).
In addition, as structural unit (a1), particularly preferably comprise the structural unit that the following general formula (a1-1-01) of the structural unit of formula (a1-1-1)～formula (a1-1-4) represents or the following general formula (a1-1-02) that comprises the structural unit of formula (a1-1-35)～(a1-1-41).
[in formula, R represents hydrogen atom, low alkyl group or junior alkyl halides, R 11represent low alkyl group.]
[in formula, R represents hydrogen atom, low alkyl group or junior alkyl halides, R 12represent low alkyl group.H represents 1～3 integer.]
In general formula (a1-1-01), R is same as described above.
R 11low alkyl group identical with the low alkyl group in R, preferable methyl or ethyl.
In general formula (a1-1-02), R is same as described above.
R 12low alkyl group identical with the low alkyl group in R, preferable methyl or ethyl, most preferably ethyl.H preferably 1 or 2, most preferably 2.
As structural unit (a1), can use separately a kind, also can two or more be used in combination.
(A1), in composition, the ratio of structural unit (a1) is for being preferably 10～80 % by mole with respect to forming the general construction unit of (A1) composition, and more preferably 20～70 % by mole, further preferably 25～50 % by mole.If more than lower limit, during as anti-corrosion agent composition, can easily obtain pattern, if below higher limit, can reach balance with other structural unit.
Structural unit (a2)
Structural unit (a2) is by the derivative and next structural unit of acrylate containing containing the cyclic group of lactone.
Here refer to the cyclic group of the ring (lactonic ring) that contains a have-O-C (O)-structure, containing the cyclic group of lactone.Lactonic ring be can be regarded as a ring, in the time only having lactonic ring, is called monocycle base, in the time also having other ring structures, no matter which kind of structure is this structure be, is all called many cyclic groups.
The lactone cyclic group of structural unit (a2) can effectively improve the adaptation of resist film to substrate or the compatibility of raising and moisture developer solution in the time forming resist film with (A1) composition.
As structural unit (a2), be not particularly limited, can use structural unit arbitrarily.
Particularly, as the monocycle base containing lactone, can enumerate gamma-butyrolacton and remove 1 group after hydrogen atom.As containing many cyclic groups of lactone, can enumerate dicyclo alkane, three cycloalkanes, the tetracycloalkane with lactonic ring and remove 1 group after hydrogen atom.
As the example of structural unit (a2), more specifically, can enumerate following general formula (a2-1)～(a2-5) structural unit of expression.
[in formula, R is hydrogen atom, low alkyl group or junior alkyl halides, R ' be hydrogen atom, low alkyl group, the carbon number alkoxy that is 1～5 or-COOR "; above-mentioned R " be that hydrogen atom or carbon number are the alkyl of 1～15 straight chain shape, a chain or ring-type, m is 0 or 1 integer, A " be to contain alkylidene, oxygen atom or the sulphur atom that the carbon number of oxygen atom or sulphur atom is 1～5.]
R in general formula (a2-1)～(a2-5) is identical with the R in said structure unit (a1).
As the low alkyl group of R ', can enumerate the group identical with the low alkyl group of the R in said structure unit (a1).
As R " while being the alkyl of straight chain shape or chain, preferably carbon number is 1～10, more preferably carbon number is 1～5.
As R " while being the alkyl of ring-type, preferably carbon number is 3～15, and more preferably carbon number is 4～12, and most preferably carbon number is 5～10.Particularly, can enumerate and be replaced by fluorine atom or fluoro-alkyl or the polynaphthene such as unsubstituted mononaphthene, dicyclo alkane, three cycloalkanes, tetracycloalkane is removed more than 1 group after hydrogen atom etc.Specifically can enumerate the polynaphthenes such as the mononaphthene such as cyclopentane, cyclohexane or diamantane, norbornane, isoborneol alkane, tristane, Fourth Ring dodecane and remove more than 1 group after hydrogen atom etc.
Consider industrial acquisition easiness etc., the R ' in general formula (a2-1)～(a2-5) is hydrogen atom preferably.
As A " the carbon number that can contain oxygen atom or the sulphur atom alkylidene that is 1～5, specifically can enumerate methylene, ethylidene, positive propylidene, isopropylidene ,-O-CH 2-,-CH 2-O-CH 2-,-S-CH 2-,-CH 2-S-CH 2-etc.
Below, illustrate the concrete structure unit of above-mentioned general formula (a2-1)～(a2-5).
As structural unit (a2), be preferably selected from least a kind in the structural unit that above-mentioned general formula (a2-1)～(a2-5) represents, be more preferably selected from least a kind in the structural unit of general formula (a2-1)～(a2-3) represent.Wherein, be preferably selected from chemical formula (a2-1-1), (a2-1-2), (a2-2-1), (a2-2-2), (a2-2-9), (a2-2-10), (a2-3-1), (a2-3-2), (a2-3-9) and (a2-3-10) at least a kind in the structural unit that represents.
As structural unit (a2), can use separately a kind, also can two or more be used in combination.
(A1), in composition, the ratio of structural unit (a2) is to be preferably 5～60 % by mole with respect to the general construction unit that forms (A1) composition, more preferably 10～50 % by mole, and more preferably 20～50 % by mole.If more than lower limit, can fully obtain and contain the effect that structural unit (a2) produces, if below higher limit, can reach balance with other structural units.
Structural unit (a3)
Structural unit (a3) is by the derivative and next structural unit of acrylate containing containing the aliphatic alkyl of polar group.
(A1) composition has structural unit (a3), and therefore the water wettability of (A1) composition improves, and improves with the compatibility of developer solution, and the alkali dissolubility of exposure portion improves, and contributes to carry high-resolution.
As polar group, hydroxyalkyl after a part of hydrogen atom that can enumerate hydroxyl, cyano group, carboxyl, alkyl is replaced by fluorine atom etc., particularly preferably hydroxyl.
As aliphatic alkyl, can enumerate carbon number is the aliphatic alkyl (many cyclic groups) of 1～10 straight chain shape or the alkyl that props up chain (preferably alkylidene) or polycycle.As these many cyclic groups, can be from for example suitable choice for use in many cyclic groups of mentioning in a large number resin for anti-corrosion agent composition for the ArF excimer laser.The carbon number of these many cyclic groups preferably 7～30.
Wherein, the structural unit more preferably being derived by following acrylate, the many cyclic groups of aliphatics that this acrylate comprises the hydroxyalkyl after a part of hydrogen atom that contains hydroxyl, cyano group, carboxyl or alkyl is replaced by fluorine atom.As these many cyclic groups, can illustrate dicyclo alkane, three cycloalkanes, tetracycloalkane etc. and remove more than 2 group after hydrogen atom etc.Specifically can enumerate the polynaphthenes such as diamantane, norbornane, isoborneol alkane, tristane, Fourth Ring dodecane and remove more than 2 group after hydrogen atom etc.In these many cyclic groups, industrial preferred diamantane removes that more than 2 group after hydrogen atom, norbornane are removed more than 2 group after hydrogen atom, Fourth Ring dodecane is removed more than 2 group after hydrogen atom.
As structural unit (a3), when the alkyl in the aliphatic alkyl of polar functionalities is that carbon number is while being the alkyl of 1～10 straight chain shape or a chain, the structural unit preferably being derived by acrylic acid hydroxyethyl ester, in the time that this alkyl is many cyclic groups, the structural unit of the structural unit that preferably following formula (a3-1) represents, the structural unit that (a3-2) represents, (a3-3) expression.
[in formula, R is the same, and j is 1～3 integer, and k is 1～3 integer, and t ' is 1～3 integer, and l is 1～5 integer, and s is 1～3 integer.]
In formula (a3-1), j is preferably 1 or 2, and more preferably 1.In the time that j is 2, preferably 3 and 5 bondings of hydroxyl and adamantyl.In the time that j is 1, preferably 3 bondings of hydroxyl and adamantyl.
J is preferably 1, particularly preferably 3 of hydroxyl and adamantyl bondings.
In formula (a3-2), k is preferably 1.Cyano group preferably with 5 or 6 bondings of norborneol alkyl.
In formula (a3-3), t ' is preferably 1.L is preferably 1.S is preferably 1.Their preferred acrylic acid carboxyl terminals and 2-norborneol alkyl or 3-norborneol are alkyl linked.Fluoroalkyl alcohol preferably with 5 or 6 bondings of norborneol alkyl.
As structural unit (a3), can use separately a kind, also can two or more be used in combination.
(A1), in composition, the ratio of structural unit (a3) is to be preferably 5～50 % by mole with respect to the general construction unit that forms (A1) composition, more preferably 5～40 % by mole, and more preferably 5～25 % by mole.If more than lower limit, can fully obtain and contain the effect that structural unit (a3) produces, if below higher limit, can reach balance with other structural units.
Structural unit (a4)
Not damaging in the scope of effect of the present invention, (A1) composition can also contain said structure unit (a1)～(a3) in addition have other structural units (a4).
Structural unit (a4) is not as long as belonging to other structural units of said structure unit (a1)～(a3), be not particularly limited, can use known numerous structural units that use with resin for the resist of ArF excimer laser use, KrF excimer laser use (preferably ArF excimer laser is used) etc.
As structural unit (a4), the structural unit that preference is as derivative in the acrylate by the many cyclic groups of aliphatics that contain non-the dissociating property of acid etc.These many cyclic groups for example can be enumerated and the identical group of enumerating in said structure unit (a1), can use known numerous structural unit using in the resinous principle with the anti-corrosion agent compositions of (preferably ArF excimer laser with) etc. in ArF excimer laser, KrF excimer laser.
Particularly, if at least a kind of selecting from three ring decyls, adamantyl, Fourth Ring dodecyl, isoborneol alkyl, norborneol alkyl, because industrial easy acquisition etc. becomes preferably.It is that the alkyl of 1～5 straight chain shape or a chain is as substituting group that these many cyclic groups can have carbon number.
As structural unit (a4), specifically can illustrate the structure of following general formula (a4-1)～(a4-5).
[in formula, R is same as described above.]
In the time containing described structural unit (a4) in (A1) composition, (A1) ratio of the structural unit in composition (a4) is to be preferably 1～30 % by mole, more preferably 10～20 % by mole with respect to the total of the general construction unit that forms (A1) composition.
In the present invention, (A1) composition preferably contains and has structural unit (a1), (a2) and multipolymer (a3).As this multipolymer, can enumerate by structural unit (a1), (a2) and (a3) multipolymer that forms multipolymer by structural unit (a1), (a2), (a3) and (a4) forming etc.
(A1) composition can obtain by making the monomer utilization of derivative each structural unit use the known free radical polymerization etc. of the radical polymerization initiator of such as azoisobutyronitrile (AIBN) and so on to carry out polymerization.
While carrying out above-mentioned polymerization, by share for example HS-CH in (A1) composition 2-CH 2-CH 2-C (CF 3) 2the chain-transferring agent that-OH is such, can introduce endways-C (CF 3) 2-OH base.The multipolymer of so having introduced the hydroxyalkyl that a part of hydrogen atom of alkyl replaced by fluorine atom can reduce developing defect and LER (line edge roughness: line sidewall inhomogeneous concavo-convex) effectively.
(A1) the matter average molecular weight (Mw) of composition (the polystyrene conversion benchmark that gel permeation chromatography obtains) is not particularly limited, and preferably 2000～50000, more preferably 3000～30000, most preferably 5000～20000.If be less than the upper limit of this scope, while use as resist, resist solvent is had to sufficient dissolubility, if be greater than the lower limit of this scope, resistance to dry corrosion and resist pattern section shape are good.
Dispersion degree (Mw/Mn) is preferably 1.0～5.0, and more preferably 1.0～3.0, most preferably be 1.2～2.5.In addition, Mn represents number-average molecular weight.
[(A2) composition]
As (A2) composition, preferred molecular weight is in 500 above less thaies 2000 and have the low molecular compound of illustrative acid dissociation dissolution inhibition base and hydrophilic group in the explanation of above-mentioned (A1) composition.Compound after a part of hydrogen atom that specifically can enumerate the hydroxyl of the compound with multiple phenol skeletons is replaced by above-mentioned acid dissociation dissolution inhibition base.
(A2) composition is preferably as the sensitizer in g line or the i line resist of amplification type non-chemically, thermotolerance improving agent and the compound of a part of hydrogen atom of the hydroxyl of known low-molecular-weight phenolic compounds after being replaced by above-mentioned acid dissociation dissolution inhibition base, can be from these compounds choice for use arbitrarily.
As described low-molecular-weight phenolic compounds, can enumerate for example two (4-hydroxy phenyl) methane, two (2,3,4-trihydroxy phenyl) methane, 2-(4-hydroxy phenyl)-2-(4 '-hydroxy phenyl) propane, 2-(2,3,4-trihydroxy phenyl)-2-(2 ', 3 ', 4 '-trihydroxy phenyl) propane, three (4-hydroxy phenyl) methane, two (4-hydroxyl-3,5-3,5-dimethylphenyl)-2-hydroxy phenyl methane, two (4-hydroxyl-2,5-3,5-dimethylphenyl)-2-hydroxy phenyl methane, two (4-hydroxyl-3,5-3,5-dimethylphenyls)-3,4-dihydroxy benzenes methylmethane, two (4-hydroxyl-2,5-3,5-dimethylphenyls)-3,4-dihydroxy benzenes methylmethane, two (4-hydroxy-3-methyl phenyl)-3,4-dihydroxy benzenes methylmethane, two (3-cyclohexyl-4-hydroxyl-6-aminomethyl phenyl)-4-hydroxy phenyl methane, two (3-cyclohexyl-4-hydroxyl-6-aminomethyl phenyls)-3,4-dihydroxy benzenes methylmethane, 1-[1-(4-hydroxy phenyl) isopropyl]-4-[1,1-bis-(4-hydroxy phenyl) ethyl] benzene, phenol, metacresol, 2 of the formaldehyde condensation products of the phenol such as paracresol or xylenols, 3, 4 nucleomes etc.Certainly, be not limited to these.
Acid dissociation dissolution inhibition base is not subject to particular restriction yet, can enumerate above-mentioned group.
As (A) composition, can use separately a kind, also can two or more share.
In anti-corrosion agent composition of the present invention, (A) content of composition can regulate according to preformed resist thickness etc.
< (B) composition >
(B) composition contains the acid agent (B1) that forms of compound being represented by above-mentioned general formula (b1-1) and (below, is sometimes referred to as (B1) composition.)。Be somebody's turn to do (B1) composition identical with the compound (B1) of the invention described above.
(B1) composition can use one kind or two or more mixing to use.
In anti-corrosion agent composition of the present invention, (B) more than the content of (B1) composition in composition is preferably 40 quality %, more than 70 quality %, can be more preferably also 100 quality %.Most preferably be 100 quality %.If more than the lower limit of this scope, while using this anti-corrosion agent composition to form resist pattern, the photolithographic characteristics such as exploring degree, Yan Mo Chong Now, line width roughness (LWR), pattern form, exposure (EL) allowance, depth of focus (DOF) improve.
(B), in composition, the acid agent (B2) (hereinafter referred to as (B2) composition) beyond above-mentioned (B1) composition and above-mentioned (B1) composition can be share.
As (B2) composition, as long as the composition beyond above-mentioned (B1) composition, be not particularly limited, can use the chemically amplified photoresist acid agent proposing up to now.
As this acid agent, known up to now have diazomethane class acid agent, nitrobenzyl Sulfonates acid agent, imines Sulfonates acid agent, the two sulfone class acid agents etc. such as the salt such as salt compounded of iodine or sulfonium salt acid agent, sulfonation oximes acid agent, dialkyl group or diaryl sulphonyl diazomethane class, poly-(disulfonyl) diazomethane class multiple.
As salt acid agent, can use for example following general formula (b-1) or (b-2) represent compound.
[in formula, R 1"～R 3", R 5"～R 6" represent independently respectively aryl or alkyl; R in formula (b-1) 1"～R 3" in any 2 mutually bonding and with Cheng Huan together with sulphur atom in formula; R 4" represent straight chain shape, prop up alkyl or the fluoro-alkyl of chain or ring-type; R 1"～R 3" at least one represent aryl, R 5"～R 6" at least one represent aryl.]
R in formula (b-1) 1"～R 3" respectively with above-mentioned (b '-1) in R 1"～R 3" identical.
R 4" represent straight chain shape, prop up alkyl or the fluoro-alkyl of chain or ring-type
As the alkyl of above-mentioned straight chain shape or a chain, preferably carbon number is 1～10, and more preferably carbon number is 1～8, and most preferably carbon number is 1～4.
As the alkyl of above-mentioned ring-type, be above-mentioned R 1" cyclic group that represents, preferably carbon number is 4～15, and more preferably carbon number is 4～10, and most preferably carbon number is 6～10.
As above-mentioned fluoro-alkyl, preferably carbon number is 1～10, and more preferably carbon number is 1～8, and most preferably carbon number is 1～4.
In addition, the rate of fluoridizing (ratio of the fluorine atom in alkyl) of this fluoro-alkyl is preferably 10～100%, more preferably 50～100%, particularly the fluoro-alkyl (perfluoroalkyl) of hydrogen atom after all being replaced by fluorine atom becomes preferably because of acid strength grow.
As R 4", the most preferably alkyl of straight chain shape or ring-type or fluoro-alkyl.
R in formula (b-2) 5"～R 6" respectively with above-mentioned (b '-2) in R 5"～R 6" identical.
As the R in formula (b-2) 4", can enumerate with above formula (b-1) in R 4" identical group.
As formula (b-1), (b-2) object lesson of the salt acid agent representing, can enumerate fluoroform sulphonate or the nine fluorine fourth sulfonate of diphenyl iodine, the fluoroform sulphonate of two (4-tert-butyl-phenyl) iodine or nine fluorine fourth sulfonate, the fluoroform sulphonate of triphenylsulfonium, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate, the fluoroform sulphonate of three (4-aminomethyl phenyl) sulfonium, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate, the fluoroform sulphonate of dimethyl (4-hydroxyl naphthyl) sulfonium, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate, the fluoroform sulphonate of one phenyl dimethyl sulfonium, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate, the fluoroform sulphonate of diphenyl monomethyl sulfonium, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate, the fluoroform sulphonate of (4-aminomethyl phenyl) diphenyl sulfonium, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate, the fluoroform sulphonate of (4-methoxyphenyl) diphenyl sulfonium, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate, the fluoroform sulphonate of three (the 4-tert-butyl group) phenyl sulfonium, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate, the fluoroform sulphonate of diphenyl (1-(4-methoxyl) naphthyl) sulfonium, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate, the fluoroform sulphonate of two (1-naphthyl) phenyl sulfonium, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate, fluoroform sulphonate, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate of 1-phenyl thiophane, fluoroform sulphonate, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate of 1-(4-aminomethyl phenyl) thiophane, fluoroform sulphonate, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate of 1-(3,5-dimethyl-4-hydroxy phenyl) thiophane, fluoroform sulphonate, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate of 1-(4-methoxynaphthalene-1-yl) thiophane, fluoroform sulphonate, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate of 1-(4-ethoxy naphthalene-1-yl) thiophane, fluoroform sulphonate, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate of 1-(4-normal-butyl naphthalene-1-yl) thiophane, fluoroform sulphonate, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate of 1-phenyl tetrahydric thiapyran, fluoroform sulphonate, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate of 1-(4-hydroxy phenyl) tetrahydric thiapyran, fluoroform sulphonate, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate of 1-(3,5-dimethyl-4-hydroxy phenyl) tetrahydric thiapyran, fluoroform sulphonate, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate etc. of 1-(4-aminomethyl phenyl) tetrahydric thiapyran.
Salt after the negative ion portion that in addition, also can use these salt is replaced by mesylate, positive propane sulfonic acid salt, positive fourth sulfonate, just pungent sulfonate.
In addition, can also use above-mentioned general formula (b-1) or (b-2) in the salt acid agent (kation portion with (b-1) or (b-2) identical) of the negative ion portion that by following general formula (b-3) or (b-4) represents of negative ion portion after replacing.
[in formula, X " represent the alkylidene of the carbon number 2～6 that at least 1 hydrogen atom replaced by fluorine atom; Y ", Z " represent independently respectively the alkyl of the carbon number 1～10 that at least one hydrogen atom replaced by fluorine atom.]
X " be the alkylidene of the straight chain shape that replaced by fluorine atom of at least one hydrogen atom or a chain, the carbon number of this alkylidene is 2～6, and preferably carbon number is 3～5, and most preferably carbon number is 3.
Y ", Z " alkyl of the straight chain shape that replaced by fluorine atom at least one hydrogen atom independently respectively or a chain, the carbon number of this alkyl is 1～10, preferably carbon number is 1～7, further preferably carbon number is 1～3.
Due to the dissolubility in the resist solvent also reason such as good, X " carbon number or the Y of alkylidene ", Z " the carbon number of alkyl the smaller the better in the scope of above-mentioned carbon number.
X " alkylidene or Y ", Z " alkyl in the number of the hydrogen atom that replaced by fluorine atom more, the intensity of acid is stronger, and the transparency under high-energy light or electron ray below 200nm improves, thereby preferably.The ratio of the fluorine atom in this alkylidene or the alkyl i.e. rate of fluoridizing is preferably 70～100%, and more preferably 90～100%, preferably all hydrogen atoms are all replaced by fluorine atom the perfluorinated alkylidene or the perfluoroalkyl that obtain.
In addition, also can by have above-mentioned general formula (b-5) or (b-6) sulfonium salt of other negative ion portions beyond the kation portion and the negative ion portion that has of above-mentioned (B1) composition that represent as salt acid agent.
As above-mentioned other negative ion portions, can use the negative ion portion of the salt acid agent having proposed up to now, can enumerate for example above-mentioned general formula (b-1) or (the b-2) (R of negative ion portion of salt acid agent that represents 4" SO 3 -) etc. fluoro-alkyl azochlorosulfonate acid ion; The negative ion portion of above-mentioned general formula (b-3) or (b-4) expression etc.Wherein, preferably fluoro-alkyl azochlorosulfonate acid ion, the fluoro-alkyl azochlorosulfonate acid ion that further preferably carbon number is 1～4, the straight chain shape perfluoro alkyl sulfonic acid ion that particularly preferably carbon number is 1～4.As object lesson, can enumerate trifluoromethane sulfonic acid ion, seven fluorine n-pro-pyl azochlorosulfonate acid ions, nine fluorine normal-butyl azochlorosulfonate acid ions etc.
In this manual, sulfonation oximes acid agent refers to the compound of the group at least with 1 following general formula (B-1) expression, has acidic characteristic under the irradiation of radioactive ray.This sulfonation oximes acid agent is usually used in chemically amplified photoresist composition, therefore choice for use arbitrarily.
(in formula (B-1), R 31, R 32represent independently respectively organic group.)
R 31, R 32organic group be the group that contains carbon atom, also can there is the atom (such as hydrogen atom, oxygen atom, nitrogen-atoms, sulphur atom, halogen atom (fluorine atom, chlorine atom etc.) etc.) beyond carbon atom.
As R 31organic group, the preferably alkyl or aryl of straight chain shape, a chain or ring-type.These alkyl, aryl also can have substituting group.As this substituting group, be not particularly limited, can enumerate the alkyl of straight chain shape, a chain or ring-type that such as fluorine atom, carbon number are 1～6 etc.Here " there is substituting group ", and refer to that part or all hydrogen atom of alkyl or aryl is substituted base replacement.
As alkyl, preferably carbon number is 1～20, and further preferably carbon number is 1～10, and more preferably carbon number is 1～8, and particularly preferably carbon number is 1～6, and most preferably carbon number is 1～4.As alkyl, particularly preferably partly or entirely by the alkyl of halo (being sometimes referred to as below haloalkyl).In addition, part is referred to by the alkyl of halo the alkyl that a part of hydrogen atom is replaced by halogen atom, is referred to the alkyl that whole hydrogen atoms are replaced by halogen atom completely by the alkyl of halo.As halogen atom, can enumerate fluorine atom, chlorine atom, bromine atoms, iodine atom etc., particularly preferably fluorine atom., the preferred fluoro-alkyl of haloalkyl.
The preferred carbon number of aryl is 4～20, and more preferably carbon number is 4～10, and most preferably carbon number is 6～10.As aryl, particularly preferably partly or entirely by the aryl of halo.In addition, part is referred to by the aryl of halo the aryl that a part of hydrogen atom is replaced by halogen atom, is all referred to by the aryl of halo the aryl that whole hydrogen atoms are replaced by halogen atom.
As R 31, the alkyl that particularly preferably carbon number of unsubstituted is 1～4, or the carbon number fluoro-alkyl that is 1～4.
As R 32organic group, preferably alkyl, aryl or the cyano group of straight chain shape, a chain or ring-type.As R 32alkyl, aryl, can enumerate and above-mentioned R 31in the identical group of alkyl, aryl enumerated.
As R 32, the fluoro-alkyl that the alkyl that particularly preferably carbon number of cyano group, unsubstituted is 1～8 or carbon number are 1～8.
As sulfonation oximes acid agent, further preferred following general formula (B-2) or (B-3) compound of expression.
[in formula (B-2), R 33alkyl or the haloalkyl of cyano group, unsubstituted.R 34it is aryl.R 35alkyl or the haloalkyl of unsubstituted.]
[in formula (B-3), R 36alkyl or the haloalkyl of cyano group, unsubstituted.R 37it is the aromatic hydrocarbyl of divalent or 3 valencys.R 38alkyl or the haloalkyl of unsubstituted.P " be 2 or 3.]
In above-mentioned general formula (B-2), R 33alkyl or the preferred carbon number of haloalkyl of unsubstituted be 1～10, more preferably carbon number is 1～8, most preferably carbon number is 1～6.
As R 33, preferably haloalkyl, more preferably fluoro-alkyl.
R 33in more than 50% being replaced by fluorine of hydrogen atom of fluoro-alkyl preferred alkyl, more preferably more than 70% replaced by fluorine, particularly preferably more than 90% replaced by fluorine.
As R 34aryl, the heteroaryl after can enumerating a part that phenyl, biphenyl (biphenyl) base, fluorenes (fluorenyl) base, naphthyl, anthracene (anthryl) base, phenanthryl etc. remove 1 group after hydrogen atom by aromatic hydrocarbon ring and form the carbon atom of the ring of these groups and being replaced by heteroatomss such as oxygen atom, sulphur atom, nitrogen-atoms etc.Wherein, preferred fluorenyl.
R 34aryl can to have carbon number be the substituting groups such as 1～10 alkyl, haloalkyl, alkoxy.The preferred carbon number of alkyl in this substituting group or haloalkyl is 1～8, and more preferably carbon number is 1～4.In addition, the preferred fluoro-alkyl of this haloalkyl.
As R 35alkyl or the haloalkyl of unsubstituted, preferably carbon number is 1～10, more preferably carbon number is 1～8, most preferably carbon number is 1～6.
As R 35, preferably haloalkyl, more preferably fluoro-alkyl.
R 35in more than 50% being replaced by fluorine of hydrogen atom of fluoro-alkyl preferred alkyl, more preferably more than 70% replaced by fluorine, in the time more than 90% being replaced by fluorine, the sour intensity of generation improves, thereby particularly preferably.The perfluoroalkyl that most preferably hydrogen atom 100% is replaced by fluorine.
In above-mentioned general formula (B-3), as R 36alkyl or the haloalkyl of unsubstituted, can enumerate and above-mentioned R 33alkyl or the identical group of haloalkyl of unsubstituted.
As R 37divalent or the aromatic hydrocarbyl of 3 valencys, can enumerate by above-mentioned R 34aryl further remove the group after 1 or 2 hydrogen atoms.
As R 38alkyl or the haloalkyl of unsubstituted, can enumerate and above-mentioned R 35alkyl or the identical group of haloalkyl of unsubstituted.
P " preferably 2.
As the object lesson of sulfonation oximes acid agent, can enumerate α-(p-tosyloxy imido grpup)-benzyl cyanide compound, α-(p-chlorobenzene sulfonyloxy imido grpup)-benzyl cyanide compound, α-(4-nitrobenzene sulfonyloxy imido grpup)-benzyl cyanide compound, α-(4-nitro-2-trifluoromethyl phenylsulfonyloxy imido grpup)-benzyl cyanide compound, α-(phenylsulfonyloxy imido grpup)-4-chlorobenzyl prussiate, α-(phenylsulfonyloxy imido grpup)-2,4-dichloro benzyl prussiate, α-(phenylsulfonyloxy imido grpup)-2,6-dichloro benzyl prussiate, α-(phenylsulfonyloxy imido grpup)-4-methoxy-benzyl prussiate, α-(2-chlorobenzene sulfonyloxy imido grpup)-4-methoxy-benzyl prussiate, α-(phenylsulfonyloxy imido grpup)-thiophene-2-base acetonitrile, α-(4-dodecyl phenylsulfonyloxy imido grpup)-benzyl cyanide compound, α-[(p-tosyloxy imido grpup)-4-methoxyphenyl] acetonitrile, α-[(dodecyl phenylsulfonyloxy imido grpup)-4-methoxyphenyl] acetonitrile, α-(tosyloxy imines)-4-thienyl prussiate, α-(sulfonyloxy methyl oxygen base imido grpup)-1-cyclopentenyl acetonitrile, α-(sulfonyloxy methyl oxygen base imido grpup)-1-cyclohexenyl group acetonitrile, α-(sulfonyloxy methyl oxygen base imido grpup)-1-cycloheptenyl acetonitrile, α-(sulfonyloxy methyl oxygen base imido grpup)-1-cyclooctene base acetonitrile, α-(trimethyl fluoride sulfonyl oxygen base imido grpup)-1-cyclopentenyl acetonitrile, α-(trimethyl fluoride sulfonyl oxygen base imido grpup)-cyclohexyl acetonitrile, α-(ethyl sulfonyloxy imido grpup)-ethyl acetonitrile, α-(sulfonyl propyl oxygen base imido grpup)-propyl group acetonitrile, α-(cyclohexyl sulfonyloxy imido grpup)-cyclopentyl acetonitrile, α-(cyclohexyl sulfonyloxy imido grpup)-cyclohexyl acetonitrile, α-(cyclohexyl sulfonyloxy imido grpup)-1-cyclopentenyl acetonitrile, α-(ethyl sulfonyloxy imido grpup)-1-cyclopentenyl acetonitrile, α-(isopropyl sulfonyloxy imido grpup)-1-cyclopentenyl acetonitrile, α-(normal-butyl sulfonyloxy imido grpup)-1-cyclopentenyl acetonitrile, α-(ethyl sulfonyloxy imido grpup)-1-cyclohexenyl group acetonitrile, α-(n-pro-pyl sulfonyloxy imido grpup)-1-cyclohexenyl group acetonitrile, α-(normal-butyl sulfonyloxy imido grpup)-1-cyclohexenyl group acetonitrile, α-(sulfonyloxy methyl oxygen base imido grpup)-phenylacetonitrile, α-(sulfonyloxy methyl oxygen base imido grpup)-p-methoxyphenyl acetonitrile, α-(trimethyl fluoride sulfonyl oxygen base imido grpup)-phenylacetonitrile, α-(trimethyl fluoride sulfonyl oxygen base imido grpup)-p-methoxyphenyl acetonitrile, α-(ethyl sulfonyloxy imido grpup)-p-methoxyphenyl acetonitrile, α-(sulfonyl propyl oxygen base imido grpup)-p-aminomethyl phenyl acetonitrile, α-(sulfonyloxy methyl oxygen base imido grpup)-p-bromophenyl acetonitrile etc.
In addition, also can preferably use in Japanese patent laid-open 9-208554 communique ([change 18]～[the changing 19] of paragraph [0012]～[0014]) disclosed sulfonation oximes acid agent in disclosed sulfonation oximes acid agent, No. 04/074242 pamphlet of International Publication (examples 1～40 of 65th～85 pages).
Preferred example is as follows.
As the object lesson of dialkyl group in diazomethane class acid agent or diaryl sulphonyl diazomethane class, can enumerate two (isopropyl sulphonyl) diazomethane, two (tolysulfonyl) diazomethanes, two (1,1-dimethyl ethyl sulphonyl) diazomethane, two (cyclohexyl sulphonyl) diazomethane, two (2,4-3,5-dimethylphenyl sulphonyl) diazomethane etc.
In addition, also can preferably use disclosed diazomethane class acid agent in Japanese patent laid-open 11-035551 communique, Japanese patent laid-open 11-035552 communique, Japanese patent laid-open 11-035573 communique.
As poly-(disulfonyl) diazomethane class, for example can enumerate in Japanese patent laid-open 11-322707 communique disclosed 1, 3-bis-(phenyl sulphonyl dizaomethyl sulphonyl) propane, 1, 4-bis-(phenyl sulphonyl dizaomethyl sulphonyl) butane, 1, 6-bis-(phenyl sulphonyl dizaomethyl sulphonyl) hexane, 1, 10-bis-(phenyl sulphonyl dizaomethyl sulphonyl) decane, 1, 2-bis-(cyclohexyl sulphonyl dizaomethyl sulphonyl) ethane, 1, 3-bis-(cyclohexyl sulphonyl dizaomethyl sulphonyl) propane, 1, 6-bis-(cyclohexyl sulphonyl dizaomethyl sulphonyl) hexane, 1, 10-bis-(cyclohexyl sulphonyl dizaomethyl sulphonyl) decane etc.
(B2) composition can use separately a kind of above-mentioned acid agent, also can be used in combination two or more.
The content of (B) composition in anti-corrosion agent composition of the present invention, for being 0.5～30 mass parts with respect to 100 mass parts (A) composition, is preferably 1～20 mass parts.In above-mentioned scope, can fully carry out pattern formation.And, can obtain uniform solution, storage stability is good, thereby preferably.
Any composition > of <
In order to improve resist pattern form, to place ageing stability (Japanese original text: draw I Zhi き Longitude Time stability) etc., anti-corrosion agent composition of the present invention can also contain organic compounds containing nitrogen (D) (hereinafter referred to as (D) composition).
About this (D) composition, many kinds of substance has been proposed, any choice for use from known material, wherein, preferred aliphat amine, particularly preferably secondary aliphatic amine, aliphatic tertiary amine.Fatty amine refers to the amine with more than 1 fatty group, and the preferred carbon number of this fatty group is 1～12.
As fatty amine, can enumerate ammonia NH 3at least one hydrogen atom be amine (alkyl amine or alkyl alcoholamine) or the cyclammonium after alkyl below 12 or hydroxyalkyl replace by carbon number.
As the object lesson of alkyl amine and alkyl alcoholamine, can enumerate alkyl amines such as n-hexyl amine, n-heptyl amine, n-octylamine, n-nonyl amine, positive decyl amine; The dialkylamines such as diethylamide, di-n-propyl amine, two n-heptyl amine, di-n-octyl amine, dicyclohexyl amine; The trialkylamines such as Trimethylamine, triethylamine, three n-pro-pyl amine, tri-n-butyl amine, three n-pentyl amine, three n-hexyl amine, three n-heptyl amine, three n-octylamine, three n-nonyl amine, three positive decyl amine, three dodecyl amine; The alkyl alcoholamines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, two n-octyl alcohol amine, three n-octyl alcohol amine.Wherein, the trialkylamine that the alkyl that preferably 3 carbon numbers are 5～10 and nitrogen atom bonding form, most preferably three n-pentyl amine.
As cyclammonium, can enumerate and for example contain nitrogen-atoms as heteroatomic heterogeneous ring compound.As this heterogeneous ring compound, can be monocyclic compound (aliphatics monocycle amine), can be also polycyclic compund (aliphatics polycyclic amines).
As aliphatics monocycle amine, specifically can enumerate piperidines, piperazine etc.
As aliphatics polycyclic amines, preferably carbon number is 6～10, specifically can enumerate 1,5-diazo bicyclic [4.3.0]-5-nonene, 1,8-diazo bicyclic [5.4.0]-7-undecylene, urotropine, Isosorbide-5-Nitrae-diazo bicyclic [2.2.2] octane etc.
Except the above-mentioned material of enumerating, can also preferably use stearyl diethanolamine.
They may be used alone, two or more kinds can also be used in combination.
(D) composition uses conventionally with respect to 100 mass parts (A) composition in the scope of 0.01～5.0 mass parts.
In order to prevent that sensitivity from declining, improving resist pattern form, placing ageing stability etc., in anti-corrosion agent composition of the present invention, can also contain at least one compound (E) (hereinafter referred to as (E) composition) conduct composition arbitrarily in oxyacid and the derivant thereof that is selected from organic carboxyl acid and phosphorus.
As organic carboxyl acid, preference is as acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid etc.
As oxyacid and the derivant thereof of phosphorus, can enumerate phosphoric acid, phosphonic acids, phosphinic acids etc., wherein phosphonic acids particularly preferably.
As the derivant of the oxyacid of phosphorus, ester after the hydrogen atom that can enumerate such as above-mentioned oxyacid is replaced by alkyl etc., as above-mentioned alkyl, can enumerate carbon number and be 1～5 alkyl, the aryl that carbon number is 6～15 etc.
As the derivant of phosphoric acid, can enumerate the phosphate such as di(2-ethylhexyl)phosphate n-butyl, di(2-ethylhexyl)phosphate phenylester etc.
As the derivant of phosphonic acids, can enumerate the phosphonate esters such as phosphonic acids dimethyl esters, phosphonic acids di-n-butyl ester, phosphonic acids phenylester, phosphonic acids diphenyl, phosphonic acids dibenzyl ester etc.
As the derivant of phosphinic acids, can enumerate the phosphinates such as phosphinic acids phenylester etc.
(E) composition can use separately a kind, also can two or more share.
As (E) composition, preferably organic carboxyl acid, particularly preferably salicylic acid.
(E) composition uses in the ratio that with respect to 100 mass parts (A) composition is 0.01～5.0 mass parts.
As required, in anti-corrosion agent composition of the present invention, can also suitably add and there is blended adjuvant, for example for improving the additivity resin of resist film performance, for improving surfactant, dissolution inhibitor, plastifier, stabilizing agent, colorant, anti hazing agent, dyestuff of coating etc.
[organic solvent (S)]
Anti-corrosion agent composition of the present invention can be by manufacturing material dissolves in organic solvent (S) (being sometimes referred to as below (S) composition).
As (S) composition, as long as dissolving the each composition using the solvent of making homogeneous solution, can from the solvent of known chemically amplified photoresist in the past, suitably select one kind or two or more arbitrarily.
The lactone such as such as gamma-butyrolacton; The ketones such as acetone, MEK, cyclohexanone, methyl-n-amyl ketone, methyl isoamyl ketone, 2-HEPTANONE; The polyalcohols such as ethylene glycol, diglycol, propylene glycol, dipropylene glycol; Ethylene glycol acetate, diglycol monotertiary acetic acid esters, propylene glycol monoacetate or dipropylene glycol monoacetate etc. have the derivant that monoalky lether or single phenyl ethers etc. such as the monomethyl ether of the compound of ester bond, above-mentioned polyalcohols or the above-mentioned compound with ester bond, single ethylether, single propyl ether, single-butyl ether have the polyalcohols such as compound of ehter bond [wherein, preferably propylene glycol monomethyl ether (PGMEA), propylene glycol monomethyl ether (PGME)]; The cyclic ethers classes such as diox or, the ester class such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methoxy methyl propionate, ethoxyl ethyl propionate; The fragrant same clan organic solvents such as methyl phenyl ethers anisole, ethyl benzyl ether, tolyl methyl ether, diphenyl ether, dibenzyl ether, phenetol, butyl phenylate, ethylbenzene, diethylbenzene, amylbenzene, isopropyl benzene,toluene,xylene, isopropyl toluene, mesitylene etc.
These organic solvents can use separately, also can be used as mixed solvent of more than two kinds and use.
Wherein, preferred propylene glycol monomethyl ether (PGMEA), propylene glycol monomethyl ether (PGME), EL.
In addition, the mixed solvent that also preferred PGMEA and polar solvent mix.Its proportioning (mass ratio) can suitably determine according to the intermiscibility of PGMEA and polar solvent etc., preferably 1: 9～9: 1, more preferably in the scope of 2: 8～8: 2.
More specifically, in the time mixing EL as polar solvent, the mass ratio of PGMEA: EL is preferably 1: 9～and 9: 1, more preferably 2: 8～8: 2.In the time mixing PGME as polar solvent, the mass ratio of PGMEA: PGME is preferably 1: 9～and 9: 1, more preferably 2: 8～8: 2, more preferably 3: 7～7: 3.
As (S) composition, in addition, be also preferably selected from PGMEA and EL at least a kind with the mixed solvent of gamma-butyrolacton.Now, about blending ratio, the mass ratio of the former with the latter is preferably 70: 30～and 95: 5.
(S) consumption of composition is not particularly limited, for concentration that can coating on substrate etc., suitably set according to coated film thickness, conventionally, taking the solid component concentration of anti-corrosion agent composition as 2～20 quality %, preferably use in the scope of 5～15 quality %.
The anti-corrosion agent composition of the invention described above is in the past unknown new compositions.
Contain compound of the present invention (b1-1) as acid agent, photolithographic characteristics be can improve, for example, exploring degree while forming resist pattern, mask reappearance (such as mask linearity etc.), exposure (EL) allowance, resist pattern form, depth of focus (DOF) etc. improved.
EL holds nargin and refers to when change exposure is exposed, can be so that the size in specialized range forms the scope of the exposure of resist pattern with the deviation of target size, obtain the scope of the exposure of the resist pattern of faithful to mask pattern, the value that EL holds nargin is larger, the variable quantity of the pattern dimension producing with the variation of exposure is less, the appearance nargin of operation improves, thereby preferably.
Infer and produce the reasons are as follows of above-mentioned effect., the negative ion portion of above-claimed cpd (b0-1) has at " Y 1-SO 3-" skeleton on bonding have R x-Q 3-O-Q 2-structure.Therefore, compared with the fluoro-alkyl azochlorosulfonate acid ion in the past using as negative ion, polarity is large, sterically hindered large, becomes huge structure.By inference, compared with the negative ion portion of the existing acid agents such as nine fluorine fourth azochlorosulfonate acid ions, the intermolecular interaction that polarity causes greatly with and huge spatial structure can suppress chemically and physically this diffusion of negative ion portion (acid) in resist film.Therefore, the acid that suppresses exposure area generation is spread to unexposed area, thereby poor (the dissolving contrast) of the dissolubility to alkaline developer of unexposed area and exposure area improved, and takes this, and exploring degree and resist pattern form improve.
Y 1can there is substituent alkylidene and maybe can have compared with the alkyl chain of substituent fluoro alkylidene and perfluoroalkyl chain that for example carbon number is 6～10 hard-decomposed, its decomposability is good, can obtain and consider that the operability of the biosome property accumulated further improves this effect.
" resist pattern formation method "
The resist pattern formation method of the present invention's the 2nd mode comprise with anti-corrosion agent composition of the present invention on supporter, form the operation of resist film, by the operation of above-mentioned resist film exposure and above-mentioned resist film is carried out to the operation that alkali develops to form resist pattern.
This resist pattern formation method for example can carry out as follows.
; first on supporter, be coated with the anti-corrosion agent composition of the invention described above with spin coater etc.; under the temperature conditions of 80～150 DEG C; prebake conditions (postapply bake:PAB) 40～120 seconds; preferably 60～90 seconds, utilize such as ArF exposure device etc., undertaken after selectivity exposure by ArF excimer laser by required mask pattern; under the temperature conditions of 80～150 DEG C, implement 40～120 seconds, preferred 60～90 seconds PEB (heating after exposure).Then, use alkaline developer, for example 0.1～10 quality % Tetramethylammonium hydroxide (TMAH) aqueous solution to carry out alkali development treatment to it, preferably use pure water to carry out water wash, dry.According to circumstances, also can after above-mentioned alkali development treatment, toast processing (baking afterwards).Like this, can obtain the resist pattern of faithful to mask pattern.
As supporter, be not particularly limited, can use known supporter in the past, such as substrate for electronic device, be formed with this substrate of the wiring pattern of regulation etc.More specifically, can enumerate metal substrate or the glass substrates etc. such as silicon wafer, copper, chromium, iron, aluminium.As the material of wiring pattern, can use such as copper, aluminium, nickel, gold etc.
As supporter, it can also be the substrate that is provided with mineral-type and/or organic film on aforesaid substrate.As the film of mineral-type, can enumerate inorganic antireflection film (inorganic BARC).As the film of organic, can enumerate organic antireflection film (organic BARC).
The wavelength that exposure adopts is not subject to particular restriction, can adopt ArF excimer laser, KrF excimer laser, F 2excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron ray), X ray, grenz ray isoradial carry out.Above-mentioned anti-corrosion agent composition is to KrF excimer laser, ArF excimer laser, EB or EUV, particularly ArF excimer laser is effective.
The exposure of resist film can be the common exposure (dry type exposure) of carrying out in the inert gas such as air or nitrogen, can be also immersion exposure.
If employing immersion exposure, described above, in when exposure, be that part between the resist film on the lens and the wafer that make to be full of the inert gas such as air or nitrogen impregnated under the state of the solvent (immersion medium) that refractive index is greater than air refraction and exposes in the past.
More specifically, immersion exposure is that the solvent (immersion medium) that uses refractive index to be greater than air refraction is full of the resist film obtaining as stated above and is positioned between the lens of exposure device below, under this state, by required mask pattern expose (impregnated exposure).
As immersion medium, preferred index is greater than air refraction and is less than the solvent of the refractive index of the resist film being exposed by this impregnated exposure.As the refractive index of described solvent, as long as in above-mentioned scope, be not particularly limited.
Be greater than air refraction and be less than the solvent of the refractive index of resist film as refractive index, can enumerate such as water, fluorine class inert fluid, silicone based solvent, varsol etc.
As the object lesson of fluorine class inert fluid, can enumerate with C 3hCl 2f 5, C 4f 9oCH 3, C 4f 9oC 2h 5, C 5h 3f 7the liquid that is principal ingredient Deng fluoride compound etc., preferably boiling point is the liquid of 70～180 DEG C, further the preferred liquid of 80～160 DEG C.If fluorine class inert fluid has the boiling point of above-mentioned scope,, after end exposure, can remove the medium using in immersion by simple method, thereby become preferably.
As fluorine class inert fluid, the all-fluoroalkyl compound that particularly preferably hydrogen atom of alkyl is all replaced by fluorine atom.As all-fluoroalkyl compound, specifically can enumerate perfluoroalkyl ether compound or perfluoroalkyl amines.
More specifically, as above-mentioned perfluoroalkyl ether compound, perfluor (2-butyl-tetrahydrofuran) (102 DEG C of boiling points) can be enumerated, as above-mentioned perfluoroalkyl amines, perfluor tri-butylamine (174 DEG C of boiling points) can be enumerated.
Embodiment
, illustrate in greater detail the present invention by embodiment below, but the invention is not restricted to these embodiment.
In following example, the compound that chemical formula (II) is represented is designated as " compound (II) ", and the compound of other chemical formulations is also explained with the same manner respectively.
[synthesis example 1]
94.1%), 2-benzyl oxyethanol 3.14g, toluene 43.4g pack compound (II) 4.34g (purity:, add p-toluenesulfonic acid monohydrate 0.47g, reflux 20 hours at 105 DEG C.By reacting liquid filtering, in screening, add hexane 20g, stir.Refilter, screening is dry, obtain compound (III) 1.41g (yield: 43.1%).
The compound obtaining (III) is carried out to NMR analysis.
1H-NMR(DMSO-d6，400MHz)：δ(ppm)＝4.74-4.83(t，1H，OH)、4.18-4.22(t，2H，H a)、3.59-3.64(q，2H，H b)。
19F-NMR(DMSO-d6、376MHz)：δ(ppm)＝-106.6。
The above results confirms: under compound (III) has, show structure.
[embodiment 1]
In compound (III) 1.00g and acetonitrile 3.00g, at ice-cooled lower dropping 1-diamantane formyl chloride 0.82g and triethylamine 0.397g.After dropping finishes, at room temperature stir 20 hours, filter.By filtrate concentrate drying, be dissolved in methylene chloride 30g, wash 3 times.By organic layer concentrate drying, obtain compound (IV) 0.82g (yield: 41%).
The compound obtaining (IV) is carried out to NMR analysis.
1h-NMR (DMSO-d6,400MHz): δ (ppm)=8.81 (s, 1H, H c) 4.37-4.44 (t, 2H, H d), 4.17-4.26 (t, 2H, H e), 3.03-3.15 (q, 6H, H b), 1.61-1.98 (m, 15H, diamantane), 1.10-1.24 (t, 9H, H a).
19F-NMR(DMSO-d6，376MHz)：δ(ppm)＝-106.6。
The above results confirms: under compound (IV) has, show structure.
[embodiment 2]
94.1%), 2-benzyl oxyethanol 3.14g, toluene 43.4g pack compound (II) 4.34g (purity: into, add p-toluenesulfonic acid monohydrate 0.47g, at 105 DEG C, reflux after 20 hours, cooling, then add triethylamine hydrochloride 3.18g, at room temperature stir 3 hours.In reactant liquor, add methylene chloride 31.4g, filter.By filtrate concentrate drying, obtain compound (VII) 1.31g (yield: 19.8%).
The compound obtaining (VII) is carried out to NMR analysis.
1H-NMR(DMSO-d6、400MHz)：δ(ppm)＝9.20(s，1H，H c)、4.80(s，1H，H f)、4.19-4.21(t，2H，H d)、3.58-3.59(m，2H，H e)、3.04-3.10(q，6H，H b)、1.13-1.21(t，9H，H a)。
19F-NMR(DMSO-d6，376MHz)：δ(ppm)＝-106.6。
The above results confirms: under compound (VII) has, show structure.
[embodiment 3]
In compound (VII) 1.33g and acetonitrile 3.00g, at ice-cooled lower dropping 1-diamantane formyl chloride 0.82g and triethylamine 0.397g.After dropping finishes, at room temperature stir 20 hours, filter.By filtrate concentrate drying, be dissolved in methylene chloride 30g, wash 3 times.By organic solvent layer concentrate drying, obtain compound (IV ') 0.86g (yield: 43.1%).
The compound obtaining (IV ') is carried out to NMR analysis.Obtain the spectrogram identical with the compound (IV) obtaining in [embodiment 1].
[embodiment 4]
Compound (V) 0.384g is dissolved in to methylene chloride 3.84g and water 3.84g, adds compound (IV) 0.40g.Stir after 1 hour, reclaim organic layer by separatory processing, water 3.84g washing 3 times.By the organic layer concentrate drying obtaining, obtain compound (VI) 0.44g (yield 81.5%).
The compound obtaining (VI) is carried out to NMR analysis.
1h-NMR (DMSO-d6,400MHz): δ (ppm)=7.57-7.87 (m, 14H, phenyl), 4.40-4.42 (t, 2H, H b), 4.15-4.22 (t, 2H, H a), 2.43 (s, 3H, H c), 1.60-1.93 (m, 15H, diamantane).
19F-NMR(DMSO-d6，376MHz)：δ(ppm)＝-106.6。
The above results confirms: under compound (VI) has, show structure.
[embodiment 5]
(i)
To methane-sulforic acid 60.75g a small amount of phosphorous oxide 8.53g, 2,5-xylenol 8.81g and the diphenyl sulfoxide 12.2g of adding being respectively controlled at below 20 DEG C.When temperature is controlled to 15～20 DEG C, slaking 30 minutes, is then warming up to 40 DEG C, slaking 2 hours.Then, reactant liquor is splashed into and be cooled in 15 DEG C of following pure water 109.35g.After dropping finishes, add methylene chloride 54.68g, after stirring, reclaim dichloromethane layer.
In another container, pack the hexane 386.86g of 20～25 DEG C into, drip dichloromethane layer.After dropping finishes, slaking 30 minutes at 20～25 DEG C, filters, and obtains target compound (i) 17.14g (yield 70.9%).
The compound obtaining (i) is carried out to NMR analysis.
1h-NMR (DMSO-d6,600MHz): δ (ppm)=7.61-7.72 (m, 10H, phenyl), 7.14 (s, 2H, H c), 3.12 (s, 3H, H b), 2.22 (s, 6H, H a).
The above results can confirm that compound (i) shows structure under having.
(ii)
Compound (i) 4g is dissolved in to methylene chloride 79.8g.After confirming to dissolve, add sal tartari 6.87g, add bromoacetic acid methyl adamantane 3.42g.Reflux lower reaction after 24 hours, filter, washing, carries out partial crystallization with hexane.By the powder drying under reduced pressure obtaining, obtain target compound (ii) 3.98g (yield 66%).
The compound obtaining (ii) is carried out to NMR analysis.
1h-NMR (CDCl 3, 400MHz): δ (ppm)=7.83-7.86 (m, 4H, phenyl), 7.69-7.78 (m, 6H, phenyl), 7.51 (s, 2H, H d), 4.46 (s, 2H, H c), 2.39 (s, 6H, H a), 2.33 (s, 2H, diamantane), 2.17 (s, 2H, diamantane), 1.71-1.98 (m, 11H, diamantane), 1.68 (s, 3H, H b), 1.57-1.61 (m, 2H, diamantane).
The above results can confirm that compound (ii) shows structure under having.
(iii)
Compound (ii) 4.77g is dissolved in to methylene chloride 23.83g and water 23.83g, adds compound (IV) 3.22g.Stir after 1 hour, reclaim organic layer by separatory processing, water 3.84g washing 3 times.By the organic layer concentrate drying obtaining, obtain compound (X) 4.98g (yield 87%).
The compound obtaining (X) is carried out to NMR analysis.
1h-NMR (DMSO-d6,400MHz): δ (ppm)=7.76-7.88 (m, 10H, phenyl), 7.62 (s, 2H, phenyl), 4.64 (s, 2H, H b), 4.43-4.44 (t, 2H, H e), 4.22-4.23 (t, 2H, H d), 1.51-2.36 (m, 38H, diamantane+H a+ H c).
19F-NMR(DMSO-d6、376MHz)：δ(ppm)＝-106.6。
The above results confirms: under compound (X) has, show structure.
[embodiment 6]
In reaction vessel, pack triethylamine hydrochloride 1.99g and acetonitrile 25.00g into, add wherein compound (VIII) 5.00g.At room temperature stir 15 hours, by reacting liquid filtering, filtrate is under reduced pressure heated up in a steamer to desolventizing.The material obtaining is dissolved in methylene chloride (29g) again, with pure water (5.8g) washing 2 times.By organic phase separatory, be added drop-wise in hexane (435g), obtain target compound (IX) 1.2g (yield 20%).
The compound obtaining (IX) is carried out to NMR analysis.
1h-NMR (DMSO-d6,400MHz): δ (ppm)=8.81 (brs, 1H, NH), 5.46 (t, 1H, oxo norborene), 4.97 (s, 1H, oxo norborene), 4.71 (d, 1H, oxo norborene), 4.57 (d, 1H, oxo norborene), 3.09 (q, 6H, NCH 2), 2.69-2.73 (m, 1H, oxo norborene), 2.06-2.16 (m, 2H, oxo norborene), 1.15 (t, 9H, CH 3).
19F-NMR(DMSO-d6，376MHz)：δ(ppm)＝-107.1。
The above results confirms that compound (IX) has said structure.
[embodiment 7]
In compound (III) 2.42g and acetonitrile 7.26g, at ice-cooled lower dropping 11 phosgene 2.19g and triethylamine 1.01g.
After dropping finishes, at room temperature stir 20 hours, filter.By filtrate concentrate drying, be dissolved in methylene chloride 20g, wash 3 times.By organic layer concentrate drying, obtain compound (XI) 3.41g (yield: 80.4%).
The compound obtaining (XI) is carried out to NMR analysis.
1H-NMR(DMSO-d6，400MHz)：δ(ppm)＝8.81(s，1H，H f)、4.39-4.41(t，2H，H d)、4.23-4.39(t，2H，H e)、3.06-3.10(q，6H，H h)、2.24-2.29(t，2H，H c)、1.09-1.51(m，25H，H b+H g)、0.83-0.89(t，3H，H a)。
19F-NMR(DMSO-d6，376MHz)：δ(ppm)＝-106.8。
The above results confirms that compound (XI) shows structure under having.
[embodiment 8]
Compound (XII ') 1.68g is dissolved in to methylene chloride 8.41g and water 8.41g, adds compound (XI) 2.00g.Stir after 1 hour, reclaim organic layer by separatory processing, water 3.84g washing 3 times.By the organic layer concentrate drying obtaining, obtain compound (XII) 2.20g (yield 81.5%).
The compound obtaining (XII) is carried out to NMR analysis.
1h-NMR (DMSO-d6,400MHz): δ (ppm)=7.74-7.90 (m, 15H, phenyl), 4.39-4.42 (t, 2H, H e), 4.21-4.24 (t, 2H, H d), 2.25-2.89 (t, 3H, H c), 1.17-1.50 (m, 15H, H b), 0.79-0.88 (t, 3H, H a).
19F-NMR(DMSO-d6，376MHz)：δ(ppm)＝-106.8。
The above results confirms that compound (XII) shows structure under having.
[embodiment 9]
Triethylamine hydrochloride 2.50g, compound (XIII) 3.19g, acetonitrile 15.00g are at room temperature stirred 15 hours.By reacting liquid filtering, filtrate is under reduced pressure heated up in a steamer to desolventizing, obtain compound (XIV) 4.01g (yield 95.6%).
The compound obtaining (XIV) is carried out to NMR analysis.
1H-NMR(DMSO-d6，400MHz)：δ(ppm)＝9.20(s，1H，H c)、3.02-3.13(q，6H，H b)、1.11-1.24(t，9H，H a)。
19F-NMR(DMSO-d6，376MHz)：δ(ppm)＝-106.8。
The above results confirms that compound (XIV) shows structure under having.
[embodiment 10, comparative example 1]
Each composition shown in table 1 is mixed, dissolved, the anti-corrosion agent composition of preparation eurymeric.
[table 1]
The meaning of the each abbreviation in table 1 is as follows.In addition, the numerical value in [] in table 1 is blending amount (mass parts).
In addition, in table 1, (B)-1 9.14 weight portions are equimolar amounts with 8.0 mass parts of (B ')-1.
(A)-1: the Mw=7000 that following chemical formula (A)-1 (in formula, l/m/n=45/35/20 (mol ratio)) represents, the multipolymer of Mw/Mn=1.8.
(B)-1: the compound (above-claimed cpd (VI)) that following chemical formula (B)-1 represents.
(B ')-1: following chemical formula (B ')-1 compound representing.
(D)-1: three n-pentyl amine.
(E)-1: salicylic acid.
(S)-1: gamma-butyrolacton.
(S)-2:PGMEA/PGME=6/4 (mass ratio).
The anti-corrosion agent composition that use obtains carries out following evaluation.
[formation of resist pattern]
On the silicon wafer of 8 inches, with spin coater coating organic antireflection film composition " ARC29A " (trade name, Bu Li science (Block リ ユ ワ mono-サ イ エ Application ス) company's system), on heating plate, at 205 DEG C, sintering makes it dry for 60 seconds, forms the organic antireflection film of thickness 82nm.Then, on this antireflection film, be coated with respectively above-mentioned anti-corrosion agent composition with spin coater, on heating plate, under the condition of 110 DEG C, 60 seconds, carry out prebake conditions (PAB) and process, dry, form the resist film of thickness 150nm.
Then,, for above-mentioned resist film, (NIKON manufactures to utilize ArF exposure device NSR-S302; NA (opening number)=0.60,2/3 ring illumination), across mask pattern, elective irradiation ArF excimer laser (193nm).Then, after exposing at 110 DEG C, under the condition of 60 seconds, heating (PEB) is processed, then at 23 DEG C, Tetramethylammonium hydroxide (TMAH) aqueous solution with 2.38 quality % is developed 30 seconds, then uses pure water drip washing 30 seconds, and water dumping is dry.
Consequently, line and the space pattern (hereinafter referred to as L/S pattern) of live width 120nm, spacing 240nm in arbitrary example, all on above-mentioned resist film, have been formed.
Obtain the suitableeest exposure Eop (mJ/cm of the L/S pattern that forms above-mentioned live width 120nm, spacing 240nm 2).In addition, as exploring degree, obtain the boundary exploring degree in above-mentioned Eop.They the results are shown in table 2.
Use scanning electron microscope (trade name: S-9220, company of Hitachi system) to observe the section shape of the L/S pattern of live width 120nm, the spacing 240nm of above-mentioned formation.Consequently, the resist pattern form of embodiment 10 is compared with comparative example 1, and the perpendicularity of line sidewall improves, and is suppressed etc. rectangularity raising with the limit (Japanese original text: the full front of a Chinese gown draws I) of dragging of substrate interface.
[LWR evaluation]
For the L/S pattern of the live width 120nm, the spacing 240nm that form with above-mentioned Eop, utilize and survey long SEM (scanning electron microscope, accelerating potential 800V, trade name: S-9220, company of Hitachi system), length direction along the line is measured the live width at 5 places, calculates 3 times of values (3s) of standard deviation (s) as the yardstick that represents LWR from its result.Its result is as shown in table 2.The value of this 3s is less, represents that the roughness of live width is less, obtains the more L/S pattern of homogeneous of width.
[EL holds nargin]
Except changing respectively exposure, adopt sequence of operation similar to the above, form the L/S pattern taking live width 120nm, spacing 240nm as target size.
Now, obtain with target size (live width 120nm) ± 5% (114nm, 126nm) exposure while forming the line of L/S pattern, then obtain EL with following formula and hold nargin (unit: %).Its result is as shown in table 2.
EL holds in nargin (%)=(| E1-E2|/Eop) × 100[formula, exposure (mJ/cm when E1 represents to form the L/S pattern of live width 114nm 2), exposure (mJ/cm when E2 represents to form the L/S pattern of live width 126nm 2).]
[table 2]
Embodiment 10 Comparative example 1
Eop(mJ/cm 2) 36.0 31.5
Exploring degree (nm) 110 110
LWR(nm) 8.1 10.4
EL allowance (%) 7.37 5.70
[mask error factor (MEF) evaluation]
With above-mentioned Eop, use taking the L/S pattern of live width 130nm, spacing 260nm as the mask pattern of target and mask taking the L/S pattern of live width 120nm, spacing 260nm as target, form L/S pattern, obtained the value of MEF by following formula.
MEF＝|CD 130-CD 120|/|MD 130-MD 120|
In above formula, CD 130, CD 120it is respectively the actual linewidth (nm) that uses the L/S pattern of the mask pattern formation taking live width 130nm, 120nm as target.MD 130, MD 120respectively the target live width (nm) of this mask pattern, MD 130=130, MD 120=120.The value of this MEF more approaches 1, represents the more faithful to mask of resist pattern forming.
Consequently, embodiment 10 is 2.0, and comparative example 1 is 2.0, equal.
[mask linear evaluation]
With above-mentioned Eop, the L/S of mask pattern is fixed on to 1: 1 than (ratio that live width is wide with space), make mask size (live width) in the scope of 110～150nm taking 10nm as Unit alteration, form respectively L/S pattern, measure the size (live width) of the L/S pattern forming.Its result is as shown in table 3.
As shown in table 3, in embodiment 10, under the Eop of 120nm, even if size departs from 120nm, compared with comparative example 1, also can form the L/S pattern of the size of faithful to mask size, prove that the mask reappearance of the anti-corrosion agent composition of embodiment 10 is better than the anti-corrosion agent composition of comparative example 1.
[table 3]
Embodiment 10 Comparative example 1
110nm 93.5 89.5
120nm 121.9 119.9
130nm 118.8 139.1
140nm 147.4 153.1
150nm 163.2 167.0
As shown in the above results, the photolithographic characteristics excellence of the anti-corrosion agent composition of embodiment 10.
[embodiment 11～13, comparative example 2]
Each composition shown in table 4 is mixed, dissolved, the anti-corrosion agent composition of preparation eurymeric.
[table 4]
(A)-1 in table 4, (D)-1, (S)-1, (S)-2 are identical with (A)-1, (D)-1, (S)-1, (S-2) in table 1, the meaning that other abbreviation is expressed as follows respectively.In addition, the numerical value in [] is blending amount (mass parts).
In addition, the blending amount (total) of (B) composition of embodiment 11～13 and comparative example 2 is respectively equimolar amounts.
(B)-2: under show chemical formula (B)-2 represent compound (above-claimed cpd (X)).
(B ')-2: following chemical formula (B ')-2 compounds that represent.
The anti-corrosion agent composition that use obtains carries out following evaluation.
[formation of resist pattern]
On the silicon wafer of 8 inches, with spin coater coating organic antireflection film composition " ARC29A " (trade name, Bu Li scientific company system), on heating plate, at 205 DEG C, sintering makes it dry for 60 seconds, forms the organic antireflection film of thickness 89nm.Then, on this antireflection film, be coated with respectively above-mentioned anti-corrosion agent composition with spin coater, on heating plate, under the condition of 110 DEG C, 60 seconds, carry out prebake conditions (PAB) and process, dry, form the resist film of thickness 150nm.
Then, use spin coater on above-mentioned resist film, to be coated with diaphragm and form with coating fluid " TILC-035 " (trade name, Tokyo Applied Chemistry Industrial Co., Ltd.'s system), at 90 DEG C, heat 60 seconds, form the outer diaphragm of thickness 90nm.
Then (NIKON manufactures, to utilize ArF liquid immersion exposure apparatus NSR-S609B; NA (opening number)=1.07, σ 0.97), across the mask of sectional hole patterns, to having formed the above-mentioned resist film elective irradiation ArF excimer laser (193nm) of outer diaphragm.
Then, after exposing at 105 DEG C, under the condition of 60 seconds, heating (PEB) is processed, then at 23 DEG C, Tetramethylammonium hydroxide (TMAH) aqueous solution with 2.38 quality % is developed 30 seconds, then uses pure water drip washing 30 seconds, and water dumping is dry.
Consequently, in arbitrary example, all on above-mentioned resist film, formed hole that bore dia is 90nm and arranged with equidistantly (spacing 180nm) contact hole pattern (hereinafter referred to as DenceCH pattern) forming.
Then, to form the suitableeest exposure Eop (mJ/cm of above-mentioned Dence CH pattern 2) to form bore dia be 90nm hole arranges with equidistantly (spacing 570nm) contact hole pattern (hereinafter referred to as Iso CH pattern) forming.
Photolithographic characteristics in the Iso CH pattern of above-mentioned diameter 90nm is evaluated.Its result is as shown in table 5.
[depth of focus (DOF) evaluation]
With above-mentioned Eop, focus is suitably staggered up and down, similarly form resist pattern with above-mentioned [formation of resist pattern], obtain the depth of focus (DOF, unit: nm) that can form above-mentioned Iso CH pattern in the scope of the size changing rate of target size ± 5% (i.e. 85.5～94.5nm).Its result is as shown in table 5.
[MEF evaluation]
With above-mentioned Eop, adopt respectively the mask pattern that the target size of bore dia is decided to be to 61nm, 63nm, 65nm, 67nm, 69nm, form the Iso CH pattern of spacing 57nm.Now, obtain taking target size (nm) as transverse axis, draw as the longitudinal axis taking the aperture (nm) of the sectional hole patterns that forms with each mask pattern the slope of the straight line obtaining on resist film, as MEF.The value of MEF (slope of straight line) more approaches 1 and represents that mask reappearance is better.The result obtaining is as shown in table 5.
[EL holds nargin evaluation]
Obtain with target size (bore dia 90nm) ± 5% (85.5nm, 94.5nm) exposure while forming the Iso CH pattern of diameter 90nm, then obtain EL by following formula and hold nargin (unit: %).Its result is as shown in table 5.
EL holds in nargin (%)=(| E1-E2|/Eop) × 100[formula, exposure (mJ/cm when E1 represents to form the CH pattern of bore dia 85.5nm 2), exposure (mJ/cm when E2 represents to form the CH pattern of bore dia 94.5nm 2).]
[table 5]
Embodiment 11 Embodiment 12 Embodiment 13 Comparative example 2
Eop(mJ/cm 2) 37.1 39.4 42.1 41.7
DOF(nm) 0.15 0.14 0.15 0.14
MEF 3.03 3.32 2.98 3.52
EL holds nargin (%) 9.5 9.46 9.27 8.58
As shown in table 5, compared with the anti-corrosion agent composition of comparative example 2, it is good that MEF, the EL of the anti-corrosion agent composition of embodiment 11～13 holds nargin, better on DOF.
The above results confirms: the intermediate that the compound (b0-1) of the present invention's the 6th mode can be served as acid agent compound uses, and the compound (b1-1) of the present invention's the 3rd mode is to serve as the compound that acid agent uses.
[embodiment 14～20]
Each composition shown in table 6 is mixed, dissolved, the anti-corrosion agent composition of preparation eurymeric.
[table 6]
(B)-1 in table 6, (D)-1, (S)-2 are identical with (B)-1, (D)-1, (S)-2 in table 1, and other abbreviations are expressed as follows respectively the meaning.Numerical value in [] is blending amount (mass parts).
In addition, the blending amount (total amount) of (B) composition of embodiment 14～20 is respectively equimolar amounts.
(A)-2: the Mw=10000 that following chemical formula (A)-2 (in formula, l/m/n=30/50/20 (mol ratio)) represents, the multipolymer of Mw/Mn=2.0.
(A)-3: the Mw=10000 that following chemical formula (A)-3 (in formula, l/m/n=40/40/20 (mol ratio)) represents, the multipolymer of Mw/Mn=2.0.
The anti-corrosion agent composition that use obtains carries out following evaluation.
[formation of resist pattern]
On the silicon wafer of 12 inches, with spin coater coating organic antireflection film composition " ARC29A " (trade name, Bu Li scientific company system), on heating plate, at 205 DEG C, sintering makes it dry for 60 seconds, forms the organic antireflection film of thickness 70nm.Then, on this antireflection film, be coated with respectively above-mentioned anti-corrosion agent composition with spin coater, on heating plate, under the condition of 110 DEG C, 60 seconds, carry out prebake conditions (PAB) and process, dry, form the resist film of thickness 170nm.
Then (NIKON manufactures, to utilize ArF exposure device NSR-S308F; NA (opening number)=0.85, σ=0.95), across mask pattern, to above-mentioned resist film elective irradiation ArF excimer laser (193nm).Then, after exposing under the condition of 90 DEG C, 60 seconds, heating (PEB) is processed, and then at 23 DEG C, Tetramethylammonium hydroxide (TMAH) aqueous solution with 2.38 quality % is developed 30 seconds, then uses pure water drip washing 30 seconds, and water dumping is dry.
Consequently, in arbitrary example, all on above-mentioned resist film, formed hole that bore dia is 110nm and arranged with equidistantly (spacing 210nm) the Dense CH pattern forming.
Then, to form the suitableeest exposure Eop (mJ/cm of above-mentioned Dence CH pattern 2) to form bore dia be 110nm hole arranges with equidistantly (spacing 780nm) the Iso CH pattern forming.
Photolithographic characteristics in the each CH pattern of Dense/Iso to above-mentioned diameter 110nm is evaluated.Its result is as shown in table 7.
[depth of focus (DOF) evaluation]
With above-mentioned Eop, focus is suitably staggered up and down, similarly form resist pattern with above-mentioned [formation of resist pattern], obtain the depth of focus (DOF, unit: nm) that can form above-mentioned each CH pattern in the scope of the size changing rate of target size ± 5% (i.e. 104.5～115.5nm).
[MEF evaluation]
The target size that adopts respectively bore dia is the mask pattern taking 1nm as unit change in the scope of 110nm ± 5nm, with above-mentioned Eop, forms each CH pattern (spacing is Dense:210nm, Iso:780nm).Now, obtain taking mask size (nm) as transverse axis, draw as the longitudinal axis taking the aperture (nm) of the sectional hole patterns that forms with each mask pattern the slope of the straight line obtaining on resist film, as MEF.The value of MEF (slope of straight line) more approaches 1 and represents that mask reappearance is better.
[CDU (homogeneity of bore dia) evaluation]
To the each CH pattern obtaining, measure respectively the diameter (Dence:54, Iso:26) in hole, obtain 3 times of values (3 σ) of the standard deviation (σ) being calculated by this result.The value of 3 σ that so try to achieve is less, and the CDU that is formed at the each hole on this resist film is higher, means that the deviation of the diameter that is present in the hole in certain limit is less.
[roundness evaluation]
Use the long SEM of survey (company of Hitachi system, ProductName: S-9220) to observe the hole shape in each CH pattern, evaluate by following benchmark.
A: circularity very high (circumferential part of the sectional hole patterns of observing from overhead does not have concavo-convex, and shape is very good).
B: circularity high (circumferential part of the sectional hole patterns of observing from overhead is slightly concavo-convex, and entirety is the shape that circularity is high)
[table 7]
As shown in table 7, the anti-corrosion agent composition of embodiment 14～20 has excellent photolithographic characteristics (DOF, MEF, CDU, circularity) at Dense/Iso CH pattern two Fang Jun.About the hole shape of CDU and circularity etc., the anti-corrosion agent composition of embodiment 15～19 is good especially.
The above results also confirms: the intermediate that the compound (b0-1) of the present invention's the 6th mode can be served as acid agent compound uses, and the compound (b1-1) of the present invention's the 3rd mode is to serve as the compound that acid agent uses.
[embodiment 21]
To in compound (III) 8.00g and methylene chloride 150.00g at ice-cooled lower dropping 1-diamantane acetyl chloride 7.02g and triethylamine 3.18g.After dropping finishes, at room temperature stir 20 hours, filter.Filtrate, with pure water 54.6g washing 3 times, by organic layer concentrate drying, is obtained to compound (XV) 14.90g (yield: 88.0%).
The compound obtaining (X V) is carried out to NMR analysis.
1h-NMR (DMSO, 400MHz): δ (ppm)=8.81 (brs, 1H, H c), 4.40 (t, 2H, H d), 4.20 (t, 2H, H e), 3.08 (q, 6H, H b), 2.05 (s, 2H, H f), 1.53-1.95 (m, 15H, diamantane), 1.17 (t, 9H, H a).
19F-NMR(DMSO，376MHz)：δ(ppm)＝-106.90。
The above results confirms that compound (XV) shows structure under having.
[embodiment 22]
Compound (V) 7.04g is dissolved in methylene chloride 70.4g and water 70.4g, adds compound (XV) 9.27g.Stir after 1 hour, reclaim organic layer by separatory processing, with 1%HClaq 70.4g washing 1 time, with pure water 70.4g washing 4 times.By the organic layer concentrate drying obtaining, obtain compound (XVI) 11.59g (yield 90.6%).
The compound obtaining (XVI) is carried out to NMR analysis.
1h-NMR (DMSO, 400MHz): δ (ppm)=7.50-7.87 (m, 14H, phenyl), 4.42 (s, 3H, H c), 4.23 (s, 2H, H b), 2.43 (s, 3H, H a), 2.01 (s, 2H, H f), 1.94 (s, 2H, diamantane), 1.52-1.61 (m, 13H, diamantane)
19F-NMR(DMSO，376MHz)：δ(ppm)＝-106.49
The above results confirms that compound (XVI) shows structure under having.
[embodiment 23]
Compound (XX) 21.6g, water 53.0g and methylene chloride 69.7g are at room temperature stirred, add wherein compound (IV) 12.9g.Stir after 1 hour, reclaim organic layer by separatory, with 1%HCl aq 34.9g washing 1 time, with pure water 69.7g washing 2 times.By the organic layer concentrate drying obtaining, obtain compound (XXI) 9.94g (yield 61.4%).
The compound obtaining (XXI) is carried out to NMR analysis.
1h-NMR (DMSO, 400MHz): δ (ppm)=8.00 (d, 2H, H f), 7.75 (t, 1H, H i), 7.58 (t, 2H, H g), 5.30 (s, 2H, H e), 4.37-4.44 (t, 2H, H a), 4.17-4.26 (t, 2H, H b), 3.54 (m, 4H, H d), 2.49-2.18 (m, 4H, H c), 1.93-1.60 (m, 15H, diamantane)
19F-NMR(DMSO，376MHz)：δ(ppm)＝-106.2
The above results confirms that compound (XXI) shows structure under having.
[embodiment 24～26]
Each composition shown in table 8 is mixed, dissolved, prepare the anti-corrosion agent composition of eurymeric.
[table 8]
(B)-1, (S)-2 in table 8 are identical with (B)-1, (S)-2 in table 1, and other abbreviations represent respectively the following meaning.Numerical value in [] is blending amount (mass parts).
In addition, the blending amount (total amount) of (B) composition of embodiment 24～26 is respectively equimolar amounts.
(A)-4: the Mw=10000 that following chemical formula (A)-4 (in formula, l/m/n=30/50/20 (mol ratio)) represents, the multipolymer of Mw/Mn=2.0.
(A)-5: the Mw=10000 that following chemical formula (A)-5 (in formula, l/m/n=30/50/20 (mol ratio)) represents, the multipolymer of Mw/Mn=2.0.
(A)-6: macromolecular compound (A)-6 (synthesizing by aftermentioned reference example 3).
(B)-3: the compound (above-claimed cpd (XVI)) that following chemical formula (B)-3 represents.
(B)-4: the compound (above-claimed cpd (XXI)) that following chemical formula (B)-4 represents.
(D)-2: stearyl diethanolamine.
[synthesis example of macromolecular compound (A)-6]
[reference example 1]
In the there-necked flask of 1L, pack sodium hydride (NaH) 4.8g into, in ice bath, keep in 0 DEG C, add 300g tetrahydrofuran (THF), then stir while add 124g compound (1), stir 10 minutes.Then, stir while add 30g compound (2), react 12 hours.After reaction finishes, by reactant liquor suction filtration, remove the THF in the filtrate of recovery by reduced pressure concentration.Then, in concentrate, add water and ethyl acetate to extract, by the ethyl acetate solution reduced pressure concentration obtaining, with column chromatography (SiO 2, heptane: ethyl acetate=8: 2) refine, by fraction reduced pressure concentration, and then drying under reduced pressure, obtain compound (3) 12g.
The compound (3) that mensuration obtains 1h-NMR.Its result is as follows.
1h-NMR (solvent: CDCl 3, 400MHz): δ (ppm)=4.09 (s, 2H (H a)), 3.75 (t, 2H (H b)), 3.68 (t, 2H (H c)), 3.03 (brs, 2H (H d)), 1.51-2.35 (m, 17H (H e))
The above results confirms that compound (3) shows structure under having.
[reference example 2]
In the there-necked flask of 300mL, pack 5g compound (3), 3.04g triethylamine (Et into 3n) and 10g THF, stir 10 minutes.Then, add 2.09g compound (4) and 10g THF, at room temperature react 12 hours.After reaction finishes, by reactant liquor suction filtration, remove the THF in the filtrate of recovery by reduced pressure concentration.Then, in concentrate, add water and ethyl acetate to extract.To the column chromatography (SiO for ethyl acetate solution obtaining 2, heptane: ethyl acetate=8: 2) refine, by fraction reduced pressure concentration, and then drying under reduced pressure, obtain compound (5) 4.9g.
The compound (5) that mensuration obtains 1h-NMR.Its result is as follows.
1h-NMR (solvent: CDCl 3, 400MHz): δ (ppm)=6.15 (s, 1H (H a)), 5.58 (s, 1H (H b)), 4.35 (t, 2H (H c)), 4.08 (s, 2H (H d)), 3.80 (t, 2H (H e)), 1.51-2.35 (m, 2OH (H f))
The above results confirms that compound (5) shows structure under having.
[reference example 3 (synthesizing of macromolecular compound (A)-6)]
The compound (5) of the compound of 6.30g (30.30mmol) (6), 7.00g (20.83mmol), 2.83g (11.99mmol) compound (7) are dissolved in to 64.52g MEK.In this solution, add with the pure medicine of light V-601 processed (polymerization initiator) 11.68mmol and make its dissolving.It is spent and within 6 hours, be added drop-wise in the MEK 26.88g that is heated to 75 DEG C under nitrogen atmosphere gas.After dropping finishes, reactant liquor is added to thermal agitation 1 hour, then, reactant liquor is cooled to room temperature.
It is 30 quality % that this polymer fluid is concentrated into solid constituent, is at room temperature added drop-wise in the normal heptane of 320mL multipolymer is separated out.Then, prepare the THF solution 54g of this multipolymer, be added drop-wise in normal heptane 320mL multipolymer is separated out.
With the mixed solution of methanol/water=60/40 (volume ratio), this multipolymer is disperseed and carry out the washing of multipolymer, then use the mixed solution of methanol/water=70/30 (volume ratio) disperse and carry out the washing of multipolymer, reclaim by filtering.
The multipolymer so obtaining is dried to 3 days at 40 DEG C, obtains 12.0g white powder (yield 74%).
The copolymer sheet obtaining is shown to macromolecular compound (A)-6, and its structural formula is as follows.Measure this macromolecular compound (A)-6 13c-NMR (600MHz), result: polymkeric substance composition (ratio (mol ratio) of the each structural unit in following structural formula) is l/m/n=52.6/27.5/19.9.The matter average molecular weight (Mw) of measuring the polystyrene standard conversion of trying to achieve by GPC is 5300, and dispersion degree (Mw/Mn) is 1.97.This result proves: the macromolecular compound (A)-the 6th obtaining, the multipolymer of compound (6) and compound (5) and compound (7).
The anti-corrosion agent composition that use obtains, forms resist pattern by following sequence of operation, evaluates photolithographic characteristics.
[formation of resist pattern]
On the silicon wafer of 12 inches, with spin coater coating organic antireflection film composition " ARC29 " (trade name, Bu Li scientific company system), on heating plate, at 205 DEG C, sintering makes it dry for 60 seconds, forms the organic antireflection film of thickness 89nm.Then, on this antireflection film, be coated with respectively the eurymeric anti-corrosion agent composition of embodiment 24～26 obtained above with spin coater, on heating plate, under the condition of 90 DEG C, 60 seconds, carry out prebake conditions (PAB) and process, dry, the resist film of formation thickness 120nm.
Then, use spin coater on above-mentioned resist film, to be coated with diaphragm and form with coating fluid " TSRC-002 " (trade name, Tokyo Applied Chemistry Industrial Co., Ltd.'s system), at 90 DEG C, heat 60 seconds, form the outer diaphragm of thickness 28nm.
Then,, for the above-mentioned resist film that has formed outer diaphragm, (NIKON manufactures to utilize immersion ArF exposure device NSR-S609B; NA (opening number)=1.07,2/3 ring illumination, 1/4 times of minification, immersion medium: water), across mask pattern (6% shadow tone) elective irradiation ArF excimer laser (193nm).
Then; using diaphragm to remove liquid " TS-Rememover-S " (trade name, Tokyo Applied Chemistry Industrial Co., Ltd.'s system) removes after outer diaphragm; carry out under the conditions shown in Table 8 PEB processing; then at 23 DEG C, TMAH aqueous solution NMD-W (trade name, Tokyo Applied Chemistry Industrial Co., Ltd.'s system) alkali with 2.38 quality % develops 30 seconds; then use pure water drip washing 25 seconds, water dumping is dry.
Consequently, in arbitrary example, all having formed diameter is the CH pattern that 70nm, spacing are 131nm.The suitableeest exposure Eop (mJ/cm now 2) be that sensitivity is as shown in table 9.
[roundness evaluation]
Use the long SEM of survey (company of Hitachi system, ProductName: S-9220) to observe the hole shape in each CH pattern, evaluate with the benchmark identical with embodiment 14～20.Result is as shown in table 9.
[table 9]
Embodiment 24 Embodiment 25 Embodiment 26
Eop(mJ/cm 2) 31 28 20
Circularity A B B
The result of table 9 confirms: the intermediate that the compound (b0-1) of the present invention's the 6th mode can be served as acid agent compound uses, and the compound (b1-1) of the present invention's the 3rd mode is the compound that can serve as acid agent.

Claims (10)

1. an anti-corrosion agent composition, it is contain the base material component that the dissolubility to alkaline developer changes under sour effect (A) and by the anti-corrosion agent composition of the acidic acid agent composition (B) that exposes to, it is characterized in that,
Described acid agent composition (B) contains the acid agent (B1) being formed by the compound of following general formula (b1-1-1) expression,
In formula, R xit is the saturated hydrocarbyl of the straight chain shape of unsubstituted carbon number 1～20; R 1for alkylidene;
Y 1that carbon number is 1～4 alkylidene or fluoro alkylidene; Z +be organic cation, but be not the ion that following general formula (w-1) represents,
In formula, R 3～R 6maybe can there is substituent alkyl for hydrogen atom independently respectively, R 3～R 6in at least 1 be described alkyl, R 3～R 6in at least 2 can be bonded to respectively ring.
2. anti-corrosion agent composition according to claim 1, wherein, described base material component (A) is the base material component under sour effect, the dissolubility of alkaline developer being increased.
3. anti-corrosion agent composition according to claim 2, wherein, described base material component (A) contains the resinous principle (A1) under sour effect, the dissolubility of alkaline developer being increased, and this resinous principle (A1) has structural unit (a1) derivative by the acrylate that contains acid dissociation dissolution inhibition base and that come.
4. anti-corrosion agent composition according to claim 3, wherein, described resinous principle (A1) also has by the derivative and next structural unit (a2) of acrylate containing containing the cyclic group of lactone.
5. anti-corrosion agent composition according to claim 3, wherein, described resinous principle (A1) also has the structural unit (a3) derivative and next by the acrylate of the aliphatic alkyl that contains polar functionalities.
6. anti-corrosion agent composition according to claim 1, it also contains organic compounds containing nitrogen (D).
7. a resist pattern formation method, it comprises: the anti-corrosion agent composition in right to use requirement 1～6 described in any one forms the operation of resist film on supporter; By the operation of described resist film exposure; And described resist film is carried out to the operation that alkali develops to form resist pattern.
8. a compound, its by following general formula (b1-1-1) represent,
In formula, R xit is the saturated hydrocarbyl of the straight chain shape of unsubstituted carbon number 1～20; R 1for alkylidene; Y 1that carbon number is 1～4 alkylidene or fluoro alkylidene; Z +be organic cation, but be not the ion that following general formula (w-1) represents,
In formula, R 3～R 6maybe can there is substituent alkyl for hydrogen atom independently respectively, R 3～R 6in at least 1 be described alkyl, R 3～R 6in at least 2 can be bonded to respectively ring.
9. the manufacture method of a compound, it comprises: the operation of reacting the compound (b1-1-1) that obtains following general formula (b1-1-1) expression by the compound (b0-02) that the compound (b0-01) of following general formula (b0-01) expression is represented with following general formula (b0-02)
In formula, R xit is the saturated hydrocarbyl of the straight chain shape of unsubstituted carbon number 1～20;
R 1for alkylidene; Y 1that carbon number is 1～4 alkylidene or fluoro alkylidene; W +it is the ion that alkali metal ion or following general formula (w-1) represent; Z +be organic cation, but be not the ion that following general formula (w-1) represents; A -non-nucleophilicity negative ion,
In formula, R 3～R 6maybe can there is substituent alkyl for hydrogen atom independently respectively, R 3～R 6in at least 1 be described alkyl, R 3～R 6in at least 2 can be bonded to respectively ring.
10. an acid agent, it is formed by compound claimed in claim 8.
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